Supplementary Material

Highly selective extraction of uranium from

nitric acid medium with phosphine oxide

functionalized pillar[5]arenes in room

temperature ionic liquid

Lixi Chen Ying Wang Xiangyang Yuan Yi Ren Ning Liu Lihua Yuan and Wen Feng

Institute of Nuclear Science and Technology Key Laboratory for Radiation

Physics and Technology of Ministry of Education College of Chemistry Sichuan

University Chengdu 610064 China

Fig S1 Partial 2D NOESY spectrum (400 MHz chloroform-d6 298 K mixing time

= 03 s) of L-I (150 mM) and C8minNTf2 (150 mM)

Fig S2 UV-vis spectrophotometric titration of L-I (10 times 10-4 M) with C8minNTf2 (0-

50 equiv) in CHCl3 at 298 K

Fig S3 Determination of the binding constant of L-I (10 times 10-4 M) and C8minNTf2

(0-50 equiv) in CHCl3 at 298 K Fitting result based on the absorbance at 288 nm

Fig S4 Job plots for the complexation of L-I and C8minNTf2 in CHCl3 based on the

absorbance at 288 nm indicating a 11 stoichiometry The total concentration is 30 times

10-3 M

Fig S5 HRESI-MS spectrum of the L-I and the 11 complex formed between L-I

and C8mim+ Inset (a) experimental isotope distribution of [L-I sup Na]+ (b) computer

simulation of [L-I sup Na]+ (c) experimental isotope distribution of [L-I sup C8mim]+

(d) computer simulation of [L-I sup C8mim]+

Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model

of L-I The structure L-I was optimized by the density functional theory (DFT)

method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+

C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue

= N) All terminal phenyl groups of each chain in the host molecule are replaced by

methyl groups for simplicity and hydrogens except the ones involved in hydrogen

bonding between host and guest are omitted for clarity The dashed pink lines in (b)

indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring

(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =

3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange

lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =

4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =

4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =

3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was

optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)

level by employing the Gaussian 09 program [1]

Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S1 Partial 2D NOESY spectrum (400 MHz chloroform-d6 298 K mixing time

= 03 s) of L-I (150 mM) and C8minNTf2 (150 mM)

Fig S2 UV-vis spectrophotometric titration of L-I (10 times 10-4 M) with C8minNTf2 (0-

50 equiv) in CHCl3 at 298 K

Fig S3 Determination of the binding constant of L-I (10 times 10-4 M) and C8minNTf2

(0-50 equiv) in CHCl3 at 298 K Fitting result based on the absorbance at 288 nm

Fig S4 Job plots for the complexation of L-I and C8minNTf2 in CHCl3 based on the

absorbance at 288 nm indicating a 11 stoichiometry The total concentration is 30 times

10-3 M

Fig S5 HRESI-MS spectrum of the L-I and the 11 complex formed between L-I

and C8mim+ Inset (a) experimental isotope distribution of [L-I sup Na]+ (b) computer

simulation of [L-I sup Na]+ (c) experimental isotope distribution of [L-I sup C8mim]+

(d) computer simulation of [L-I sup C8mim]+

Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model

of L-I The structure L-I was optimized by the density functional theory (DFT)

method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+

C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue

= N) All terminal phenyl groups of each chain in the host molecule are replaced by

methyl groups for simplicity and hydrogens except the ones involved in hydrogen

bonding between host and guest are omitted for clarity The dashed pink lines in (b)

indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring

(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =

3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange

lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =

4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =

4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =

3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was

optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)

level by employing the Gaussian 09 program [1]

Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S2 UV-vis spectrophotometric titration of L-I (10 times 10-4 M) with C8minNTf2 (0-

50 equiv) in CHCl3 at 298 K

Fig S3 Determination of the binding constant of L-I (10 times 10-4 M) and C8minNTf2

(0-50 equiv) in CHCl3 at 298 K Fitting result based on the absorbance at 288 nm

Fig S4 Job plots for the complexation of L-I and C8minNTf2 in CHCl3 based on the

absorbance at 288 nm indicating a 11 stoichiometry The total concentration is 30 times

10-3 M

Fig S5 HRESI-MS spectrum of the L-I and the 11 complex formed between L-I

and C8mim+ Inset (a) experimental isotope distribution of [L-I sup Na]+ (b) computer

simulation of [L-I sup Na]+ (c) experimental isotope distribution of [L-I sup C8mim]+

(d) computer simulation of [L-I sup C8mim]+

Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model

of L-I The structure L-I was optimized by the density functional theory (DFT)

method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+

C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue

= N) All terminal phenyl groups of each chain in the host molecule are replaced by

methyl groups for simplicity and hydrogens except the ones involved in hydrogen

bonding between host and guest are omitted for clarity The dashed pink lines in (b)

indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring

(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =

3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange

lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =

4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =

4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =

3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was

optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)

level by employing the Gaussian 09 program [1]

Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S3 Determination of the binding constant of L-I (10 times 10-4 M) and C8minNTf2

(0-50 equiv) in CHCl3 at 298 K Fitting result based on the absorbance at 288 nm

Fig S4 Job plots for the complexation of L-I and C8minNTf2 in CHCl3 based on the

absorbance at 288 nm indicating a 11 stoichiometry The total concentration is 30 times

10-3 M

Fig S5 HRESI-MS spectrum of the L-I and the 11 complex formed between L-I

and C8mim+ Inset (a) experimental isotope distribution of [L-I sup Na]+ (b) computer

simulation of [L-I sup Na]+ (c) experimental isotope distribution of [L-I sup C8mim]+

(d) computer simulation of [L-I sup C8mim]+

Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model

of L-I The structure L-I was optimized by the density functional theory (DFT)

method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+

C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue

= N) All terminal phenyl groups of each chain in the host molecule are replaced by

methyl groups for simplicity and hydrogens except the ones involved in hydrogen

bonding between host and guest are omitted for clarity The dashed pink lines in (b)

indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring

(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =

3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange

lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =

4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =

4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =

3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was

optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)

level by employing the Gaussian 09 program [1]

Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S4 Job plots for the complexation of L-I and C8minNTf2 in CHCl3 based on the

absorbance at 288 nm indicating a 11 stoichiometry The total concentration is 30 times

10-3 M

Fig S5 HRESI-MS spectrum of the L-I and the 11 complex formed between L-I

and C8mim+ Inset (a) experimental isotope distribution of [L-I sup Na]+ (b) computer

simulation of [L-I sup Na]+ (c) experimental isotope distribution of [L-I sup C8mim]+

(d) computer simulation of [L-I sup C8mim]+

Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model

of L-I The structure L-I was optimized by the density functional theory (DFT)

method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+

C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue

= N) All terminal phenyl groups of each chain in the host molecule are replaced by

methyl groups for simplicity and hydrogens except the ones involved in hydrogen

bonding between host and guest are omitted for clarity The dashed pink lines in (b)

indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring

(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =

3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange

lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =

4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =

4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =

3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was

optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)

level by employing the Gaussian 09 program [1]

Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S5 HRESI-MS spectrum of the L-I and the 11 complex formed between L-I

and C8mim+ Inset (a) experimental isotope distribution of [L-I sup Na]+ (b) computer

simulation of [L-I sup Na]+ (c) experimental isotope distribution of [L-I sup C8mim]+

(d) computer simulation of [L-I sup C8mim]+

Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model

of L-I The structure L-I was optimized by the density functional theory (DFT)

method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+

C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue

= N) All terminal phenyl groups of each chain in the host molecule are replaced by

methyl groups for simplicity and hydrogens except the ones involved in hydrogen

bonding between host and guest are omitted for clarity The dashed pink lines in (b)

indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring

(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =

3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange

lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =

4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =

4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =

3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was

optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)

level by employing the Gaussian 09 program [1]

Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S6 (a) Chemical structure of L-I and (b) Geometry optimized molecular model

of L-I The structure L-I was optimized by the density functional theory (DFT)

method at the B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+

C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue

= N) All terminal phenyl groups of each chain in the host molecule are replaced by

methyl groups for simplicity and hydrogens except the ones involved in hydrogen

bonding between host and guest are omitted for clarity The dashed pink lines in (b)

indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring

(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =

3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange

lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =

4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =

4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =

3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was

optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)

level by employing the Gaussian 09 program [1]

Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S7 Four side views (a) (b) (c) and (d) of optimized geometry of L-I sup C2mim+

C2mim+ is accommodated in the cavity of L-I (green = C white = H red = O and blue

= N) All terminal phenyl groups of each chain in the host molecule are replaced by

methyl groups for simplicity and hydrogens except the ones involved in hydrogen

bonding between host and guest are omitted for clarity The dashed pink lines in (b)

indicate intermolecular H-bonds A-H with A = 2557 Aring (14680deg) B = 2546 Aring

(16157deg) C = 2185 Aring (16742deg) D = 2318 Aring (15012deg) E = 2236 Aring (16436deg) F =

3017 Aring (12194deg) G = 3091 Aring (10879deg) H = 2386 Aring (16385deg) The dashed orange

lines in (c) indicate the N+O interaction I-Q with I = 4352 Aring J = 4167 Aring K =

4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =

4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =

3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was

optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)

level by employing the Gaussian 09 program [1]

Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

4065 Aring L = 4309 Aring M = 4123 Aring N = 4379 Aring O = 4329 Aring P = 4245 Aring Q =

4368 Aring The dashed yellow lines in (d) indicate the C-Hπ interaction R-U with R =

3018 Aring (13853deg) S = 2910 Aring (14709deg) The complex structure L-I sup C2mim+ was

optimized by the density functional theory (DFT) method at the B3LYP6-31G (d p)

level by employing the Gaussian 09 program [1]

Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S8 UV-vis spectrophotometric titration of L-I (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S9 Determination of the binding constant of L-I (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S10 UV-vis spectrophotometric titration of L-II (50 times 10-5 M) with

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K

Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S11 Determination of the binding constant of L-II (50 times 10-5 M) and

UO2(NO3)2middot6H2O (0-60 equiv) in CH3OHH2O (491 vv) at 298 K Fitting result

based on the absorbance at 259 nm

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S12 Job plots for the complexation of L-I and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S13 Job plots for the complexation of L-II and UO2(NO3)2middot6H2O in CH3OHH2O

(491 vv) based on the absorbance at 259 nm indicating a 11 stoichiometry The

total concentration is 10 times 10-4 M

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S14 Side view (a) and top view (b) of the optimized geometry of the hostndashguest

complex of L-I and uranyl ion using B3LYP method (green = C white = H red = O

and orange = P the guest uranyl ion is in the space filling model) The 6-31G(dp)

basis set has been used for light atoms (H C O and P) while the relativistic atomic

natural orbital (ANO) has been employed for uranium as reported [2] All terminal

phenyl groups of each chain in the host molecule L-I are replaced by methyl groups

for simplicity The dashed cyan lines in (b) indicate the coordination distances and

angles between oxygen and uranium A = 2877 Aring (1367deg) B = 2873 Aring (1364deg) C =

2868 Aring (1367deg) D = 2872 Aring (1369deg) E = 2883 Aring (1367deg)

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S15 Dependency of UO22+ distribution ratio (DU) on C8mim+ concentration with

L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5 times 10-4 M [HNO3] = 01

M

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S16 Dependency of UO22+ extraction percentage () on NTf2

- concentration in

the aqueous phase with L-I in the C8mimNTf2 aq or = 11 at 25 plusmn 10 degC [L-I] = 5

times 10-4 M [HNO3] = 01 M

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Fig S17 The separation factors for UO22+ extraction by using L-I L-II and L-III (5

times 10-4 M) from an aqueous solution with mixed metal ions (UO22+ Lu3+ Th4+ Eu3+

Yb3+ Gd3+ Pr3+ La3+ Ce3+ Sm3+ Nd3+ and Er3+ each at 10 times 10-4 M and 12 times 10-3 M

in total) at 10 M HNO3

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

The structure L-I was optimized by the density functional theory (DFT) method at the

B3LYP 6-31G (d p) level by employing the Gaussian 09 program [1]

Table S1 Atomic coordinates for the optimized structure of L-I

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 00197870 -43323960 02559940

2 C 12205250 -41410940 -04459780

3 C 11868990 -37634610 -17918270

4 C -00166870 -35643790 -24733650

5 C -12173790 -37661360 -17742800

6 C -11837820 -41458110 -04290290

7 C 00030500 -46867650 17343950

8 C -00002810 -30968900 -39199560

9 O -23917240 -35743320 -24761350

10 O 23948890 -43444920 02524550

11 C -36055940 -38742020 -17934450

12 C -47771560 -36604000 -27451190

13 P -63445210 -42232170 -19580650

14 C 36088510 -42412490 -04859000

15 C 47805280 -45527850 04382430

16 P 63497370 -46135900 -05242480

17 C -76805060 -35566480 -30014400

18 C 76835320 -45847660 07158560

19 C 00168870 -15814840 -40403960

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

20 C 12178010 -08549970 -40739910

21 C 11844180 05416310 -41324020

22 C -00190360 12515170 -41558730

23 C -12199100 05245210 -41327500

24 C -11865250 -08721680 -40769380

25 C -00020840 27717930 -41598980

26 O -23944170 12509230 -41698100

27 O 23920200 -15823970 -40491290

28 C -36078230 05077820 -42402770

29 C -47804710 14777060 -43294150

30 P -63484820 05531130 -46108440

31 C 36058980 -08485760 -41815890

32 C 47775550 -18237960 -41917010

33 P 63449460 -09291300 -45594340

34 C -76843230 17500020 -42936940

35 C 76811310 -20967310 -41481460

36 C 00186230 -10956650 41982310

37 C 12201550 -17037480 38009920

38 C 11880360 -28677230 30268720

39 C -00148030 -34553310 26260080

40 C -12162760 -28538150 30332150

41 C -11841480 -16910960 38090810

42 C 00003100 02018460 49905010

43 O -23900670 -34635170 26344910

44 O 23936780 -11011410 42109710

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

45 C -36043440 -29056590 31283220

46 C -47755950 -37457110 26317830

47 P -63437250 -31682990 34067110

48 C 36083190 -17710120 38864630

49 C 47791010 -09884940 44703490

50 P 63473010 -19260690 42362710

51 C -76795240 -39530870 24489320

52 C 76827130 -07390570 45904000

53 C 00153410 33556780 -27561450

54 C 12165320 36119400 -20759170

55 C 11836990 40976840 -07652240

56 C -00194570 43394490 -00969410

57 C -12206460 40939800 -07810200

58 C -11878340 36101060 -20924870

59 C -00018180 48101950 13485630

60 O -23943880 43539680 -01004320

61 O 23907010 33638520 -27602520

62 C -36091040 41940540 -08272740

63 C -47793740 45800050 00701650

64 P -63488730 45702540 -08936140

65 C 36047100 37155260 -21029130

66 C 47764730 34260850 -30340730

67 P 63449530 40433850 -22914950

68 C -76822130 46425430 03451750

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

69 C 76796270 32941360 -32789030

70 C 00162150 36537010 23352700

71 C 12175990 30874110 27904030

72 C 11850630 19917040 36583810

73 C -00178650 14292140 40934110

74 C -12193050 20016840 36461160

75 C -11867550 30993240 27805970

76 O -23931770 14329110 41011110

77 O 23915570 36626210 23435210

78 C -36074550 20760760 37250640

79 C -47789070 13420670 43677120

80 P -63457070 22623430 40653280

81 C 36057100 31487260 28832640

82 C 47774370 39432930 23177050

83 P 63447980 34322720 31397500

84 C -76831460 11071770 45064180

85 C 76818430 41294980 21181620

86 H 21013780 -35809300 -23403700

87 H -20980890 -42749440 01347560

88 H 08866900 -52847520 19723740

89 H -08799460 -52964110 19435320

90 H 08826990 -35085390 -44159290

91 H -08839140 -34838910 -44342640

92 H -35742700 -49153880 -14402480

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

93 H -37233920 -32316120 -09140440

94 H -46161360 -42114870 -36790820

95 H -49016470 -26016250 -29974060

96 H 35797480 -49449470 -13308140

97 H 37243230 -32337850 -09005200

98 H 46225570 -55118920 09452930

99 H 49004430 -37823160 12077990

100 H -76434870 -39943350 -40042500

101 H -75597060 -24730230 -30908310

102 H -86431070 -37964500 -25410480

103 H 86469460 -45456810 01997290

104 H 75585520 -37074320 13572870

105 H 76483200 -54816520 13426360

106 H 20988910 11197140 -41280460

107 H -21011790 -14478830 -40272330

108 H -08854910 31411920 -46873370

109 H 08811670 31154970 -47047450

110 H -35780570 -01515320 -51201970

111 H -37228600 -01286550 -33560360

112 H -46238170 21930400 -51453150

113 H -49007600 20480010 -34018110

114 H 35757330 -02643620 -51130540

115 H 37221500 -01411830 -33531900

116 H 46159270 -26065640 -49421050

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

117 H 49018910 -23121250 -32189570

118 H -86466660 12366910 -43743490

119 H -75593970 21712700 -32918820

120 H -76516670 25676000 -50209520

121 H 86436070 -15937430 -42775160

122 H 75610800 -24303490 -31132440

123 H 76437470 -29736710 -48024620

124 H 21032460 -33329090 26855320

125 H -20992450 -11959830 41055960

126 H -08830800 02122900 56343980

127 H 08835530 02448410 56332290

128 H -37215030 -18715500 27861590

129 H -35741560 -28884940 42277170

130 H -48987580 -36613230 15464600

131 H -46150000 -48036940 28701940

132 H 35787520 -27919890 42945260

133 H 37257020 -18538460 28004110

134 H 46187940 -08012950 55385990

135 H 49016970 -00192220 39746850

136 H -76441030 -50421520 25546390

137 H -75572680 -37027360 13910760

138 H -86420140 -35881380 28184560

139 H 86455540 -12205450 43975780

140 H 75605600 01396900 39504370

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

141 H 76461250 -04153020 56355440

142 H 20983550 42703960 -02138010

143 H -21026550 33853950 -26245840

144 H 08814340 54342930 15081110

145 H -08851770 54254960 15386850

146 H -37264890 31569980 -11602990

147 H -35797060 48281970 -17255700

148 H -49008730 38724970 08977400

149 H -46183110 55752260 05008530

150 H 35744440 47813370 -18328320

151 H 37214620 31440920 -11755340

152 H 46175070 39035460 -40080730

153 H 48983660 23506300 -32035770

154 H -86457820 45654330 -01663730

155 H -75594510 38181730 10537050

156 H -76447190 55856630 08997720

157 H 86426430 35676380 -28385570

158 H 75568770 22070910 -32823760

159 H 76435620 36515110 -43130950

160 H 20999720 15230270 39956620

161 H -21017010 35346680 24012850

162 H -35773080 31258160 40521740

163 H -37247030 20741310 26358330

164 H -46171740 12355000 54468020

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

165 H -49038730 03384150 39466760

166 H 35752590 32252350 39800700

167 H 37233130 20893140 26303770

168 H 46174900 50177090 24660340

169 H 49006890 37672690 12434390

170 H -86451200 15748720 42785030

171 H -75630000 01831290 39334340

172 H -76470180 08614090 55725870

173 H 86437880 37974710 25188010

174 H 75603090 37883990 10858800

175 H 76471400 52236570 21286980

176 O -64269380 -16613810 35044770

177 O -64293360 -38521810 -04943380

178 O -64270430 -07232240 -38032640

179 O -64344170 34093180 -18591090

180 O -64278780 28327560 26670580

181 C -63972220 -60407510 -22227520

182 C -64006580 -39799550 50541830

183 C -63999430 35676320 53573370

184 C -64055040 61961060 -17478930

185 C -64115670 02407970 -64205420

186 H -73385460 -64295000 -18244510

187 H -63260250 -62973240 -32837710

188 H -55746040 -65178860 -16837340

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

189 H -73428540 -37199300 55446070

190 H -63303210 -50685010 49716960

191 H -55790450 -36148060 56758530

192 H -73398400 41188950 52649850

193 H -63324760 31438620 63635820

194 H -55753370 42697720 52092640

195 H -73475220 62748580 -22976720

196 H -63349100 70277760 -10407050

197 H -55837250 62665590 -24652620

198 H -73534970 -02600360 -66609560

199 H -63455280 11700970 -69939900

200 H -55895390 -04181110 -67120880

201 O 64301200 -25980610 28839220

202 O 64311520 -35317050 -15778830

203 O 64294170 04113840 -38643350

204 O 64252960 19392080 33669930

205 O 64276530 37865630 -08033690

206 C 64039010 -31320370 56214440

207 C 64117820 -63010540 -12486040

208 C 63985100 -07724950 -63893110

209 C 64040880 58348100 -26958080

210 C 64029850 43832460 47108250

211 H 55799530 40758430 53612130

212 H 73440670 41640720 52228350

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

213 H 63357190 54607240 45340000

214 H 55832520 63551560 -21954380

215 H 73468660 62496370 -23284630

216 H 63337950 60090670 -37734800

217 H 55761200 -01386270 -67310080

218 H 73400730 -02963760 -66767300

219 H 63271100 -17470400 -68811150

220 H 55898290 -64305440 -19574770

221 H 73537650 -64189340 -17914010

222 H 63449240 -70750550 -04783760

223 H 55800580 -38441900 55264580

224 H 73444080 -36875440 55695870

225 H 63363040 -26348600 65935320

The total electronic energy is calculated to be -784883371230 au

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

The complex structure L-I sup C2mim+ was optimized by the density functional theory

(DFT) method at the B3LYP6-31G (d p) level by employing the Gaussian 09

program[1]

Table S2 Atomic coordinates for the optimized structure of [L-I∙C8mim]+

Center

number

Symbol Coordinates (Angstroms)

X Y Z

1 C 02756350 -05968500 42466050

2 C 14943700 -12276390 39439750

3 C 14903900 -24879470 33353620

4 C 03039980 -31549450 30135990

5 C -09139860 -25259580 33228950

6 C -09108470 -12637940 39282840

7 C 02232320 07832490 48832650

8 C 03630630 -45107590 23226290

9 O -20786090 -32040020 30063050

10 O 26465060 -05533880 42778630

11 C -32930310 -26373430 34939270

12 C -44598680 -35422400 31213130

13 P -60563790 -27791560 36422490

14 C 38827850 -12478390 40926180

15 C 50299590 -03708990 45771900

16 P 66180370 -13013600 44403700

17 C -73459900 -37821470 28385260

18 C 79326970 -00515940 45858410

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

19 C 03936780 -43870900 08079520

20 C 15935030 -41726210 01071830

21 C 15606510 -39583140 -12752370

22 C 03656970 -39666250 -19997740

23 C -08266020 -42308680 -13081810

24 C -07972160 -44408170 00762320

25 C 03782950 -36516840 -34873910

26 O -19929420 -42374930 -20541890

27 O 27588210 -41888090 08373520

28 C -31839550 -46534240 -13981300

29 C -43680670 -44395900 -23344230

30 P -59537860 -45830790 -14073460

31 C 39826480 -41737440 00949290

32 C 51573050 -43737580 10431300

33 P 67159460 -45011290 00626610

34 C -72555740 -41025390 -25815790

35 C 80698220 -42788610 12579670

36 C 01699130 39117250 18511990

37 C 13843530 33935450 23334030

38 C 13696580 23987390 33177480

39 C 01782900 19018440 38542890

40 C -10338080 24413970 33937070

41 C -10212550 34335260 24063690

42 C 01249060 49286700 07222230

43 O -21992030 19442680 39488490

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

44 O 25423710 39094770 17998230

45 C -34082410 26009940 35861660

46 C -45845350 19125840 42659800

47 P -61659490 27096230 37497670

48 C 37712880 35065540 24132450

49 C 49263000 42771640 17879540

50 P 64906970 38558960 26721030

51 C -74742310 15571220 42724060

52 C 78374530 44347270 15939080

53 C 03441100 -21565860 -37665030

54 C 15257200 -14052710 -38919410

55 C 14521780 -00264760 -41216640

56 C 02293610 06396460 -42376710

57 C -09504690 -01129330 -41201250

58 C -08804740 -14901860 -38834960

59 C 01976370 21447240 -44564080

60 O -21405630 05765560 -42567650

61 O 27155520 -20881890 -37824670

62 C -33421000 -01855600 -42730910

63 C -45090310 07615720 -45261350

64 P -61146420 -01416750 -44938080

65 C 39127750 -13475640 -40345380

66 C 51139850 -22784360 -39349320

67 P 66465190 -13478350 -43720710

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

68 C -73878400 11607620 -44738510

69 C 80305550 -23762850 -37913740

70 C 01860590 29201620 -31494080

71 C 13810510 32882310 -25024120

72 C 13306770 39465490 -12697820

73 C 01179620 42625500 -06454710

74 C -10701430 39074940 -13006920

75 C -10235580 32485310 -25340530

76 O -22713530 41940730 -06561380

77 O 25556670 29719050 -31399560

78 C -34213560 43775420 -14889300

79 C -45800430 48528680 -06195660

80 P -61873980 46837780 -15107420

81 C 37653550 34677540 -25570460

82 C 49448860 30979590 -34465600

83 P 64845740 38524480 -27627510

84 C -74530690 49494290 -02276110

85 C 78619480 29999430 -35908920

86 H 24186840 -29773430 30738360

87 H -18381000 -07572230 41621930

88 H 11044280 09190170 55151170

89 H -06598560 08460900 55237680

90 H 12584330 -50388540 26609210

91 H -05065850 -51042740 26160380

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

92 H -32258670 -25149180 45842460

93 H -34537930 -16463630 30558300

94 H -43509890 -45344210 35736980

95 H -45206800 -36710730 20350970

96 H 38481460 -21939050 46508630

97 H 40291880 -14912480 30351370

98 H 48678350 -00582700 56150070

99 H 51313730 05309380 39633070

100 H -72888330 -48261790 31620800

101 H -71967490 -37308970 17557930

102 H -83286440 -33804300 31005030

103 H 89016630 -05375450 44413490

104 H 77771640 07227750 38292570

105 H 79118450 04183770 55742370

106 H 24690560 -37466240 -18231850

107 H -17066210 -46367070 06302130

108 H -04836190 -41240820 -39641210

109 H 12812280 -40763930 -39329570

110 H -30957100 -57075120 -10973640

111 H -33490910 -40654990 -04898150

112 H -43445610 -51282910 -31856550

113 H -43483820 -34163590 -27266050

114 H 39489960 -49732370 -06577570

115 H 40960910 -32226490 -04356750

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

116 H 50195830 -52805190 16431340

117 H 52745310 -35274300 17289300

118 H -82292180 -41915960 -20915130

119 H -70893260 -30629370 -28844250

120 H -72410830 -47505370 -34636470

121 H 90212750 -42730790 07189700

122 H 79255030 -33343280 17898500

123 H 80775710 -50923760 19903270

124 H 22928530 19641810 36774780

125 H -19442220 38573720 20326600

126 H -07720200 55437710 08299450

127 H 09947360 55868350 07907440

128 H -35557720 25642270 25012440

129 H -33510820 36611750 38725890

130 H -46465640 08612130 39619670

131 H -44833020 19425610 53565880

132 H 37096030 37018150 34927440

133 H 39303910 24315320 22790230

134 H 47460280 53567480 18435240

135 H 50673180 40103030 07346830

136 H -74838480 14553630 53623080

137 H -72870930 05751250 38259280

138 H -84434880 19416230 39431620

139 H 87945840 41433950 20353900

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

140 H 77212970 39862590 06033410

141 H 78081250 55238980 14890880

142 H 23508680 05703890 -41982360

143 H -17811230 -20813680 -37746510

144 H 10746350 24363580 -50393430

145 H -06914060 24066570 -50353640

146 H -34846790 -07026420 -33165700

147 H -32848820 -09514160 -50597440

148 H -45610210 15267760 -37435370

149 H -43863170 12793300 -54840370

150 H 38484380 -08957180 -50344100

151 H 40189110 -05346960 -33086060

152 H 49938220 -31392890 -46024850

153 H 52460150 -26562410 -29148880

154 H -83736720 06935950 -43977690

155 H -72258290 18255460 -36195660

156 H -73458900 17528350 -53934900

157 H 89667890 -18356830 -39560700

158 H 78958880 -25910470 -27273120

159 H 80640990 -33242280 -43377500

160 H 22394340 42110700 -07465230

161 H -19360190 29525980 -30371530

162 H -31870390 50992470 -22824530

163 H -37023050 34342120 -19706100

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

164 H -44298170 58819900 -02760190

165 H -46686140 42210220 02722560

166 H 36849600 45580840 -24461930

167 H 39096090 30417150 -15588040

168 H 47808770 34471650 -44723060

169 H 51021320 20140180 -34785510

170 H -84444510 48057660 -06660380

171 H -72988630 42330040 05858570

172 H -73871390 59644290 01768210

173 H 88046120 33537550 -31641530

174 H 77570970 19211250 -34446380

175 H 78551510 32078420 -46655560

176 O -61671460 30488890 22690750

177 O -61170760 -12993940 33145330

178 O -59125970 -37581740 -01314420

179 O -61828850 -11273520 -33437550

180 O -62783850 33551620 -22352030

181 C -62182110 -31188290 54360240

182 C -63608330 41927420 48065300

183 C -63106410 61197860 -26389170

184 C -62713230 -09487530 -61320330

185 C -62068680 -63680700 -10869900

186 H -71883810 -27519960 57819850

187 H -61469280 -41892140 56493280

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

188 H -54353360 -25921930 59876600

189 H -73158100 46717750 45741460

190 H -63427400 39335360 58689120

191 H -55592960 49060760 45985170

192 H -72833260 60981990 -31377450

193 H -62088640 70658240 -20994740

194 H -55323030 60572530 -34038180

195 H -72432900 -14460890 -61916880

196 H -61940380 -02232300 -69468390

197 H -54910020 -17045950 -62521660

198 H -71739360 -65091360 -05967110

199 H -61931930 -69464220 -20153490

200 H -54256160 -67421280 -04205820

201 O 65495870 23912860 30475030

202 O 66695930 -21470930 31865480

203 O 67264900 -35427780 -11085200

204 O 65107950 38028240 -12505700

205 O 66211550 00648630 -38298380

206 C 65381490 49616860 41366990

207 C 67347390 -23035720 59731790

208 C 68220670 -62563000 -04639460

209 C 67443000 -13975150 -62040710

210 C 65208090 55680450 -34143390

211 H 56784500 61382390 -30139450

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

212 H 74459010 60510510 -30878670

213 H 64780040 55852580 -45072760

214 H 58973390 -08584440 -66366220

215 H 76646800 -09010440 -65236120

216 H 67456890 -24243700 -65811810

217 H 59933410 -64947540 -11358460

218 H 77576240 -64059170 -10099350

219 H 67971400 -69379340 03911760

220 H 59249660 -30373470 60020840

221 H 76853430 -28439200 59710740

222 H 66833970 -16782620 68692320

223 H 57083510 47263830 48083850

224 H 74734370 47935150 46776760

225 H 64786350 60157530 38500210

226 C -30556520 09069660 -00297450

227 N -42262150 02536320 -00588770

228 C -39715600 -11026370 -00134740

229 C -26138090 -12519110 00456090

230 N -20613390 00112950 00341620

231 C -06243820 03099190 00734890

232 C -55630480 09121960 -01183850

233 C -67093700 -00820670 -00216620

234 H -29190680 19788790 -00523060

235 H -47585750 -18457830 -00280540

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

236 H -19957420 -21330620 01080960

237 H -01855890 -01749040 09467110

238 H -01552550 -00588810 -08403410

239 H -04873010 13871690 01495830

240 H -56089130 16206320 07133010

241 H -56138950 14741530 -10537820

242 H -67166660 -07721620 -08684940

243 H -66822690 -06321250 09229630

244 H -76386690 04939410 -00509970

The total electronic energy is calculated to be -819347693637 au

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Table S3 Binding constants Ka and Gibbs free energies G of POP5A with

UO2(NO3)2middot6H2O in CH3OHH2O (491 vv) at 298 K

ligand L-I L-II L-III

Ka a (M-1) (26 plusmn 04) times 103 (32 plusmn 04) times 103 (60 plusmn 14) times 103b

G c (kJmol) -195 -200 -216

a The binding constants were obtained by UV-vis titration experiments

b The Ka of L-III sup UO2(NO3)2middot6H2O is from ref 3

c The Gibbs free energies (ΔG) of complexation were calculated from the Ka values

using the equation ΔG = -RT ln Ka

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

[POP5A]total

(molL)1times10-5 5times10-5 1times10-4 2times10-4 5times10-4

L-I

UIL (E) 0535 529 123 250 493

iquest 535times10-7 529times10-6 123times10-5 250times10-5 493times10-5

iquest 0946times10-5 447times10-5 0877times10-4 175times10-4 450times10-4

L-II

UIL (E) 321 267 452 673 847

iquest 321times10-6 267times10-5 452times10-5 673times10-5 847times10-5

iquest 0679times10-5 233times10-5 0548times10-4 133times10-4 415times10-4

L-

III

UIL (E) 877 340 546 739 893

iquest 877times10-6 34times10-5 546times10-5 739times10-5 893times10-5

iquest 0123times10-5 16times10-5 454times10-5 126times10-5 41times10-5

Table S4 Calculated values of (iquest)

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

The complex structure L-I sup UO22+ was optimized by the density functional theory

(DFT) method by employing the Gaussian 09 program [1]

Table S5 Atomic coordinates for the optimized structure of [L-I∙UO2]2+

Center number

SymbolCoordinates (Angstroms)

X Y Z

1 C -07160000 -28706000 32338000

2 C 04927000 -32089000 25844000

3 C 04638000 -38948000 13664000

4 C -07368000 -42523000 07535000

5 C -19497000 -39098000 13976000

6 C -19166000 -32329000 26249000

7 C -07283000 -20960000 45404000

8 C -07249000 -49634000 -05880000

9 O -31032000 -42823000 07764000

10 O 16583000 -28464000 32154000

11 C -43359000 -40442000 14796000

12 C -55070000 -45876000 06751000

13 P -70572000 -43162000 16496000

14 C 28831000 -32048000 25796000

15 C 40442000 -27535000 34599000

16 P 56602000 -31410000 26695000

17 C -84237000 -44838000 04629000

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

18 C 69536000 -25022000 37744000

19 C -07121000 -39613000 -17294000

20 C 04966000 -34493000 -22526000

21 C 04681000 -25031000 -32816000

22 C -07326000 -20298000 -38103000

23 C -19454000 -25356000 -32848000

24 C -19126000 -34931000 -22614000

25 C -07208000 -09725000 -49000000

26 O -30991000 -20594000 -38303000

27 O 16621000 -39367000 -17119000

28 C -43313000 -26569000 -33881000

29 C -55029000 -20584000 -41517000

30 P -70523000 -29071000 -35986000

31 C 28868000 -34479000 -22536000

32 C 40472000 -41461000 -15518000

33 P 56632000 -35083000 -21575000

34 C -84198000 -18286000 -41185000

35 C 69563000 -43561000 -12036000

36 C -07126000 21851000 37282000

37 C 04948000 14614000 38514000

38 C 04641000 00916000 41301000

39 C -07376000 -06001000 42796000

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

40 C -19493000 01200000 41507000

41 C -19143000 14959000 38844000

42 C -07220000 36670000 33948000

43 O -31039000 -05843000 43118000

44 O 16613000 21714000 36981000

45 C -43355000 01598000 43010000

46 C -55082000 -07721000 45663000

47 P -70568000 02408000 46114000

48 C 28852000 14583000 38589000

49 C 40467000 24334000 36960000

50 P 56618000 15593000 38116000

51 C -84244000 -09370000 43973000

52 C 69564000 28053000 35416000

53 C -07087000 04224000 -42989000

54 C 04996000 10791000 -39742000

55 C 04705000 23506000 -33936000

56 C -07303000 29996000 -31078000

57 C -19429000 23432000 -34269000

58 C -19096000 10733000 -40198000

59 C -07189000 43631000 -24396000

60 O -30970000 30096000 -31450000

61 O 16654000 04150000 -42714000

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

62 C -43284000 24032000 -35770000

63 C -55008000 33141000 -32462000

64 P -70507000 25203000 -38738000

65 C 28898000 10821000 -39746000

66 C 40504000 01975000 -44189000

67 P 56671000 09699000 -40009000

68 C -84172000 33535000 -30127000

69 C 69594000 -02010000 -45113000

70 C -07081000 42225000 -09272000

71 C 04999000 41136000 -02017000

72 C 04698000 39524000 11868000

73 C -07316000 38823000 18917000

74 C -19436000 39857000 11682000

75 C -19093000 41596000 -02225000

76 O -30978000 39231000 18886000

77 O 16661000 41890000 -09246000

78 C -43293000 41469000 11786000

79 C -55016000 41117000 21474000

80 P -70506000 44700000 11998000

81 C 28905000 41095000 -01986000

82 C 40517000 42575000 -11767000

83 P 56676000 41057000 -03099000

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

84 C -84182000 39079000 22568000

85 C 69608000 42324000 -15800000

86 H 13786000 -41540000 08514000

87 H -28335000 -29535000 31258000

88 H 01525000 -23546000 51329000

89 H -16141000 -23742000 51152000

90 H 01567000 -56060000 -06487000

91 H -16099000 -55970000 -06756000

92 H -42735000 -45321000 24609000

93 H -44683000 -29707000 16439000

94 H -53756000 -56536000 04585000

95 H -56270000 -40556000 -02755000

96 H 29104000 -42931000 24329000

97 H 29503000 -27232000 15968000

98 H 39874000 -32209000 44493000

99 H 40254000 -16664000 35858000

100 H -84719000 -55047000 00711000

101 H -82600000 -37968000 -03720000

102 H -93642000 -42517000 09703000

103 H 79300000 -28219000 33995000

104 H 68996000 -14120000 37491000

105 H 68238000 -28720000 47958000

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

106 H 13828000 -20928000 -36867000

107 H -28294000 -38815000 -18393000

108 H -16057000 -10848000 -55300000

109 H 01608000 -11120000 -55301000

110 H -42678000 -37405000 -35522000

111 H -44637000 -24850000 -23157000

112 H -53700000 -21768000 -52328000

113 H -56251000 -09911000 -39350000

114 H 29117000 -36489000 -33333000

115 H 29572000 -23642000 -21034000

116 H 39933000 -52311000 -16942000

117 H 40241000 -39339000 -04781000

118 H -93597000 -22417000 -37420000

119 H -82562000 -08239000 -37186000

120 H -84691000 -17666000 -52102000

121 H 79332000 -40948000 -16201000

122 H 68968000 -39937000 -01754000

123 H 68308000 -54423000 -12387000

124 H 13779000 -04796000 42185000

125 H -28304000 20595000 37716000

126 H -16067000 41295000 38375000

127 H 01599000 41487000 38237000

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

128 H -44654000 06486000 33308000

129 H -42735000 09418000 50690000

130 H -56288000 -15100000 37651000

131 H -53781000 -13097000 55121000

132 H 29067000 09949000 48545000

133 H 29579000 06636000 31072000

134 H 39944000 32322000 44441000

135 H 40233000 28867000 26998000

136 H -84760000 -16282000 52446000

137 H -82589000 -15158000 34843000

138 H -93640000 -03813000 43327000

139 H 79326000 23475000 37248000

140 H 68986000 31199000 24977000

141 H 68312000 36614000 42111000

142 H 13851000 28635000 -31298000

143 H -28263000 05521000 -42596000

144 H 01634000 49186000 -27663000

145 H -16032000 49281000 -27419000

146 H -44609000 14373000 -30804000

147 H -42634000 22225000 -46579000

148 H -56210000 34417000 -21644000

149 H -53706000 43041000 -36972000

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

150 H 29150000 20456000 -45016000

151 H 29598000 12765000 -28979000

152 H 39968000 -00054000 -54943000

153 H 40265000 -07565000 -38826000

154 H -93575000 28667000 -32865000

155 H -82535000 32889000 -19333000

156 H -84665000 44096000 -32963000

157 H 79365000 02752000 -43911000

158 H 68991000 -10672000 -38494000

159 H 68341000 -05025000 -55554000

160 H 13840000 38571000 17563000

161 H -28256000 42286000 -07926000

162 H -42651000 51200000 06745000

163 H -44613000 33774000 04120000

164 H -53699000 48441000 29516000

165 H -56229000 31213000 26006000

166 H 29171000 49073000 05560000

167 H 29587000 31446000 03176000

168 H 39959000 52154000 -17057000

169 H 40312000 34496000 -19150000

170 H -93584000 40210000 17097000

171 H -82560000 28603000 25258000

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

172 H -84663000 45012000 31754000

173 H 79376000 42660000 -10894000

174 H 69022000 33359000 -22003000

175 H 68346000 51327000 -21886000

176 O -69996000 13627000 35958000

177 O -70023000 -30008000 23980000

178 O -69984000 -32214000 -21181000

179 O -69951000 10164000 -37040000

180 O -69966000 38485000 -01800000

181 C -71975000 -57637000 27656000

182 C -71967000 08490000 63348000

183 C -71865000 62974000 11511000

184 C -71920000 30317000 -56283000

185 C -71895000 -44091000 -46403000

186 H -81258000 -56806000 33378000

187 H -72098000 -67043000 22071000

188 H -63630000 -57770000 34720000

189 H -81240000 14201000 64345000

190 H -72100000 00253000 70545000

191 H -63610000 15146000 65674000

192 H -81145000 65697000 06405000

193 H -71968000 67287000 21563000

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

194 H -63512000 67214000 05872000

195 H -81217000 26290000 -60400000

196 H -72019000 41206000 -57328000

197 H -63591000 26234000 -62070000

198 H -81179000 -49300000 -43899000

199 H -71996000 -41612000 -57057000

200 H -63547000 -50854000 -44372000

201 O 57224000 03778000 28484000

202 O 57293000 -25942000 12473000

203 O 57257000 -19859000 -20749000

204 O 57330000 28277000 05208000

205 O 57300000 13641000 -25282000

206 C 58451000 10441000 55570000

207 C 58361000 -49610000 27239000

208 C 58474000 -41203000 -38713000

209 C 58544000 24095000 -51137000

210 C 58479000 56103000 07143000

211 H 50885000 56370000 14995000

212 H 68342000 56054000 11863000

213 H 57582000 65130000 01030000

214 H 50954000 31660000 -48998000

215 H 68408000 28552000 -49586000

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

216 H 57691000 21083000 -61619000

217 H 50875000 -36820000 -45228000

218 H 68335000 -38362000 -42492000

219 H 57607000 -52102000 -39087000

220 H 50757000 -54422000 21042000

221 H 68217000 -52368000 23387000

222 H 57458000 -53332000 37486000

223 H 50855000 03055000 58242000

224 H 68313000 05922000 56950000

225 H 57577000 19023000 62297000

226 U 57561000 00034000 -00041000

227 O 40296000 00045000 -00078000

228 O 74727000 00016000 -00029000

The total electronic energy is calculated to be -3365085541640 au

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Table S6 Separation factor (SF) values of UO22+ with respect to other metal ions

Organic phase 5 times 10-4 M POP5A in C8mimNTf2 Aqueous phase 10-4 M for each

metal ions and 12 times 10-3 M in total concentration in 10 M HNO3

Metal ions C8mimNTf2

SFL-I SFL-II SFL-III

Sm 19times102 22times103 26times103

Ce 14times102 16times103 18times103

La 61 70times102 37times102

Pr 16times102 18times103 21times103

Er 11times102 16times103 18times103

Nd 91 10times103 12times103

Yb 23 82times102 17times102

Eu 47 54times102 62times102

Gd 31 14times103 16times103

Lu 56 15times103 32times102

Th 9 33times102 12times102

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

Table S7 Some typical phosphine oxide-based extractants for the U(VI)Th(IV)

separation

Organic phase Aqueous phase SFa Refs

29times10-4 M calix[4]arenes-based

ligand (B4boctL4) in chloroform

1times10-4 M metal ions in 1 M

HNO335 M NaNO3

11a [4]

5times10-5 M tripodal-based

phosphine oxide in 12-

dichloroethane

1times10-5 M metal ions in 4 M

NH4NO3

89 a [5]

1times10-3 M phenylphosphinate in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

17b [6]

5times10-4 M diphosphine dioxide in

12-dichloroethane

2times10-5 M metal ions in 3 M

HNO3

390b [7]

106times10-4 M calix[6]arenes-based

ligand (B6bL6) in chloroform

11times10-4 M metal ions in 3

M HNO305 M NaNO3

059 a [8]

1times10-3 M pillararenes-based

ligand (POP5A 1b) in

dichloromethane

1times10-4 M metal ions in 1 M

HNO3

135 a [9]

5times10-4 M pillararenes-based

ligand (POP5A 1b) in

C8mimNTf2

1times10-4 M metal ions in 1 M

HNO3

330 a This

work

a SF Separation factor values of UO22+ with respect to Th4+

b SF Separation factor values of Th4+ with respect to UO22+

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

References

[1] Gaussian 09 Revision B 01 MJ Frisch GW Trucks HB Schlegel GE

Scuseria MA Robb JR Cheeseman G Scalmani V Barone B Mennucci

GA Petersson H Nakatsuji M Caricato X Li HP Hratchian AF Izmaylov J

Bloino G Zheng JL Sonnenberg M Hada M Ehara K Toyota R Fukuda J

Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven JA

Montgomery Jr JE Peralta F Ogliaro MJ Bearpark J Heyd EN Brothers

KN Kudin VN Staroverov R Kobayashi J Normand K Raghavachari AP

Rendell JC Burant SS Iyengar J Tomasi M Cossi N Rega NJ Millam M

Klene JE Knox JB Cross V Bakken C Adamo J Jaramillo R Gomperts

RE Stratmann O Yazyev AJ Austin R Cammi C Pomelli JW Ochterski

RL Martin K Morokuma VG Zakrzewski GA Voth P Salvador JJ

Dannenberg S Dapprich AD Daniels Ouml Farkas JB Foresman JV Ortiz J

Cioslowski DJ Fox Gaussian Inc Wallingford CT 2010

[2] BO Roos R Lindh PAring Malmqvist V Veryazov PO Widmark New

relativistic ANO basis sets for actinide atoms Chem Phys Lett 409 (2005) 295-

299

[3] B Bai Y Fang Q Gan Y Yang L Yuan W Feng Phosphorous-based

pillar[5]arenes for uranyl extraction Chin J Chem 33 (2015) 361-367

[4] FM Ramiacuterez T Tosheva E Tashev E Garciacutea-Villafantildea S Shenkov S

Varbanov Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl

pendant arms and its complexation properties towards f-elements Polyhedron 56

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383

(2013) 123-133

[5] EV Matveeva EV Sharova AN Turanov VK Karandashev IL Odinets

Extraction properties of b-aminophosphine oxides towards lanthanides and

alkaline earth metals Cent Eur J Chem 10 (2012) 1933-1941

[6] AN Turanov VK Karandashev AN Yarkevich ZV Safronova Selectivity of

extraction of U(VI) Th(IV) and REE(III) from perchloric acid solutions with

bidentate phosphoryl-substituted butyl phenylphosphinates Radiochemistry 53

(2011) 264-268

[7] A N Turanov V K Karandashev A N Yarkevich V E Baulin Extraction of

U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (o-

phenyleneoxymethylene)diphosphine dioxides Radiochemistry 51 (2009) 359-

364

[8] FM Ramiacuterez S Varbanov J Padilla J-CG Buumlnzli Physicochemical properties

and theoretical modeling of actinide complexes with a para-tert-butylcalix[6]arene

bearing phosphinoyl pendants Extraction capability of the calixarene toward f

elements J Phys Chem B 112 (2008) 10976-10988

[9] Y Fang L Wu J Liao L Chen Y Yang N Liu L He S Zou W Feng L

Yuan Pillar[5]arene-based phosphine oxides novel ionophores for solvent

extraction separation of f-block elements from acidic media RSC Adv 3 (2013)

12376-12383