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Supporting Information
Redox Active Ligand and Metal Cooperation for C(sp2)-H Oxidation Extension of Galactose Oxidase Mechanism in Water-Mediated Amide Formation
Zahra Alajia Elham Safaeia b Hong Yic Hengjiang Congc Andrzej Wojtczakd Aiwen Leic
aInstitute for Advanced Studies in Basic Sciences (IASBS) 45137-66731 Zanjan Iran
bDepartment of Chemistry College of Sciences Shiraz University 71454 Shiraz Iran Email esafaeishirazuacir
cCollege of Chemistry and Molecular Sciences Institute for Advanced Studies (IAS) Wuhan
University Wuhan Hubei 430072 P R China Email aiwenleiwhueducn
dNicolaus Copernicus University Faculty of Chemistry 87-100 Torun Poland
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2018
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Content
Materials and Physical Methods
S3
Material Synthesis
S3
Figure S1 LC-MS spectrum of HLIPIP
S4
Figure S2 ESI-MS(HRMS) spectrum of CuLIPIP
S6
Figure S3 Molecular structure of CuIILIPIP S6
Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2
18O
S7
Figure S5 1H NMR of NiLAPIP-OH
S7
Figure S6 13 C NMR of NiLAPIP-OH
S8
Figure S7 ESI-MS(HRMS) spectrum of NiLAPIP-OH
S8
Figure S8 1H NMR of NiLAPIP crystals compare with NiLAPIP-OH
S9
Figure S9 EPR silent spectrum of NiIILAPIP
S10
Figure S10 Molecular structure of NiIILAPIP-MeO
S10
Figure S11 1H NMR of NiIILAPIP-MeO
S11
Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP
S11
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
S12
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan rate 200 mV s CH2Cl2 298 K
S12
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fc
S12
X-Ray Crystallography data of Copper Zinc and Nickel complexes
S13
S3
Materials and Physical Methods All reagents and solvents were purchased from commercial sources and were used as received unless noted otherwise Anhydrous Cu(OAc)2 98 Super dry acetonitrile dichloromethane were used for synthesis and growing crystal as mentioned Preparation and handling of air- and moisture-sensitive materials were carried out under an inert gas atmosphere of glove box NMR spectra were recorded at 400 MHz on a Bruker DRX spectrometer in CDCl3 solution The chemical shifts were referred to TMS using the residual signals from the solvent IR spectra were recorded in the solid state on a FT-IR Bruker Vector 22 spectrophotometer in the 400minus4000 cm-1 range LC-MS mass spectral data were acquired on Shimadzu LCMS 2020 HRMS spectra were recorded on thermo Fisher scientific LTQ Orbitrap Elite Cyclic Voltammetry (CV) was performed on CHI605E CH Instruments USA equipped with a Ag wire reference electrode a glassy carbon working electrode and a Pt counter electrode with 01 M Bu4N(BF4) solutions in CH2Cl2 Ferrocene was used as an internal standard
X-ray Crystallographic Analyses All crystals were placed onto the tip of a 01 mm diameter glass capillary and mounted on a Bruker SMART Platform CCD diffractometer for data collection The data collections were carried out using MoKαradiation with a graphite monochromator (λ= 071073 A) at 95 K Structure solutions were performed by direct methods using SHELXS-97 software and refined against F2using full-matrix-least-squares using SHELXL-97 and SHELXL-2013 software Data intensities were corrected for absorption and decay (SADABS) Final cell constants were obtained from least squares fits of all measured reflections All non-hydrogen atoms were refined with anisotropic displacement parameters
Material Synthesis To a solution of 35-DTBQ (35-di-tert-butylcyclohexa-35-diene-12-dione) (022 g 1 mmol) in acetonitrile (4 mL) was added 2-aminobenzyl amine (0122 g 1 mmol) and the reaction solution stirred for 30 min at the room temperature in the presence of air After some minutes it afforded a yellow precipitate (scheme S1) 1H NMR (400 MHz Chloroform-d) δ 870 (s 1H) 746 (dd 1H) 728 (dt 2H) 705 (d 1H) 679 (m 2H) 671 (s 1H) 627 (s 2H) 151 (s 9H) 140 (s 9H)
Scheme S1 Synthesis of HLAP ligand
Next to the stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1
mmol) (Scheme S2) LC-MS data clearly shows the formation of this ligand (Figure S1)
This ligand (HLIPIP) is stable at dry and inert condition When it is exposed on moisture it is hydrolyzed Therefore after one
minute stirring different metal precursors of copper zinc and nickel were added to reaction mixture to afford the metal
complexes (Scheme S3)
Scheme S2 Synthesis of HLIPIP ligand
S4
Figure S1 LC-MS spectrum of HLIPIP
Scheme 3 General scheme for the preparation of the different metal complexes
S5
Synthesis of CuIILAPIP
CuIILAPIP complex was synthesized by the following template reaction Firstly to the stirred suspension of HLAP (0324 g 1 mmol)
in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) after one minute stirring Cu(OAc)2H2O (0199 g 1
mmol) was added in the presence of 2 equivalents of NEt3 to the reaction mixture
The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate of copper complex The filtrate was left
undisturbed to afford red brown microcrystals (0309 g 63 yield) by evaporation from dichloromethaneacetonitrile solution
X-ray quality dark red single crystals were grown from a 11 solvent mixture of n-hexanedichloromethane Elemental Analysis
calculated (found) for C27H29N3O2Cu035 C6H14 C 6705 H 655 N 806 Found C 6679 H 661 N 776 νmax(KBr)cm-1 2959 (C-
H) 1642(C=O) 1466 (C=N) 802 (=C-H bending) ESI-MS mz 4912
Synthesis of CuIILIPIP
CuIILIPIP complex was synthesized by the following template reaction Firstly to a stirred suspension of HLAP (0324 g 1 mmol) in
dry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) Next Cu(OAc)2 (0181 g 1 mmol) was added to the
reaction mixture The stirring of orange-brown solution at 298 K for 4 h afforded a dark orange precipitate of copper complex
X-ray quality dark red single crystals from were grown from dry acetonitriledichloromethane ESI-MS mz ()4761751
Synthesis of CuIILAPIP-Meo
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
After one minute stirring Cu (OAc)2H2O (0199 g 1 mmol) was added in the presence of 2 equivalents of NEt3 to the reaction
mixture The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate X-ray quality dark red single
crystals were grown from a 11 solvent mixture of methanoldichloromethane
Synthesis of ZnLIPIPOAc As reported to a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1
mmol) After one minute stirring it was reacted immediately with Zn (OAc)2 2H2O (0219 g 1 mmol) to afford the zinc complex
of ZnIILIPIPOAc at the ambient temperature The stirring of black solution at 298 K for 4 h afforded a dark red-brown precipitate
X-ray quality dark crystals were grown from methanol
νmax(KBr)cm-1 3415 (OndashH) 2946 (CndashH) 1606 (C=O) 1593 (C=C) 1469 (C=N) 740 (=CndashH bending) 1H NMR (400 MHz (CD3)2SO) δ 129 (s 9H) 145 (s 9H) 159 (s 3H) 71 (d 1H) 74 (d 1H) 76 (m 2H) 78 (dd 1H) 80 (m
1H) 82 (d 1H) 84 (dt 9Hz 1H) 89 (m1H) 90(s 1H) 91(s 1H) 13C NMR (100 MHz (CD3)2SO) δ 2982 3000 3213 3221 3442 3553 10979 12103 12455 12899 12922 12963
12974 13200 13237 13354 135511385314190 145061474414999153081611716271
Synthesis of NiIILAPIP-OH
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
under N2 atmosphere (Figure S1) After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to
afford the nickel complex of NiIILAPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded
a precipitate ESI-MS mz ()4881843 1H NMR (400 MHz DMSO-d6) δ 880 (s 1H) 860 (dt J = 531 146 Hz 1H) 810 (td J = 769 157 Hz 1H) 777 (dd J = 741 184 Hz 2H) 764 (dd J = 761 522 Hz 2H) 737 (d J = 891 Hz 1H) 724 (ddd J = 873 663 174 Hz 1H) 696 (d J = 209 Hz 1H) 660 (ddd J = 775 660 097 Hz 1H) 634 (d J = 1012 Hz 1H) 607 (d J = 1006 Hz 1H) 145 (s 9H) 133 (s 9H) 13C NMR (101 MHz DMSO) δ 2976 3242 3460 3487 8840 11002 11387 11686 12066 12092 12491 13149 13454 14014 14114 14624 14821 14908 16014 16657
Synthesis of NiIILAPIP Solvent slow evaporation of NiLAPIP-OH solution from dichloromethaneacetonitrile afforded single crystal of NiIILAPIP ESI-MS mz
()4861880
Synthesis of NiIILIPIP
To a stirred suspension of HLAP (0324 g 1 mmol) in superdry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1
mmol) under N2 atmosphere After one minute stirring it was reacted immediately with Ni(OAc)2 (1 mmol 0176 g) to afford
the nickel complex of NiIILIPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded a
precipitate ESI-MS mz ()4711808
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Synthesis of NiIILAPIP-MeO
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to afford the nickel complex at the ambient temperature The stirring of dark orange solution at 298 K for 4 h afforded a precipitate X-ray quality dark crystals were grown from dichloromethanemethanol 1H NMR (400 MHz DMSO-d6) δ 885 (s 1H) 864 (ddd J = 560 154 074 Hz 1H) 817 (td J = 767 156 Hz 1H) 787 ndash 777 (m 2H) 777 ndash 765 (m 2H) 738 (d J = 884 Hz 1H) 728 (ddd J = 873 666 176 Hz 1H) 698 (d J = 206 Hz 1H) 667 (ddd J = 786 670 101 Hz 1H) 630 (s 1H) 301 (s 3H) 145 (s 9H) 133 (s 9H)
Figures and Tables
Figure S2 ESI-MS (HRMS) spectrum of CuLIPIP
Figure S3 Molecular structure of CuIILIPIP Hydrogen atoms have been omitted for clarity Thermal ellipsoids are set at 50 probability Acetonitrile molecule with the occupancy set to 50 was also found in the structure
BCL-Z5 72 RT 048 AV 1 NL 145E3T FTMS + p ESI Full ms [5000-100000]
4759 4760 4761 4762 4763 4764 4765 4766 4767
mz
0
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40
50
60
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80
90
100
Re
lative
Ab
un
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nce
4761751
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200 300 400 500 600 700 800
0
20
40
60
80
100
Rel
ativ
e In
tens
ity
mz
49345
Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2
18O
Figure S5 1H NMR of NiLAPIP- OH
S8
Figure S6 13 C NMR of NiLAPIP-OH
Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH
BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]
4877 4878 4879 4880 4881 4882 4883 4884 4885 4886
mz
0
10
20
30
40
50
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70
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90
100
Re
lative
Ab
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4881843
S9
Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)
(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to
amide)
S10
Figure S9 EPR silent spectrum of NiIILAPIP
Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are
set at 50 probability
-100000
-80000
-60000
-40000
-20000
0
20000
40000
60000
80000
100000
2500 3000 3500 4000 4500
S11
Figure S11 1H NMR of NiIILAPIP-MeO
Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP
BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]
4706 4708 4710 4712 4714 4716 4718
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
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da
nce
4711808
S12
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
compound E121 V E12
2 V
CuIILAPIP +041 -166
NiIILAPIP +051 -181
ZnIILIPIPOAc +027 -147
aPeak to peak difference for the Fc+ Fc couple at 298 K is 012
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan
rate 200 mV s CH2Cl2 298 K
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca
compound V112E V2
12E
CuIILIPIP +021 -160
NiIILIPIP +032
-189
-25 -2 -15 -1 -05 0 05 1
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X-Ray Crystallography data of Copper Zinc and nickel complexes
Table S1 Crystallographic data for CuIILAPIP
CuIILAPIP
Empirical formula C27 H29 Cu N3 O2
Formula weight 49109
Crystal system Monoclinic
Space group P1 21c 1
a (Aring) 95598(5)
b (Aring) 182903(9)
c (Aring) 141699(8)
α (deg) 90
β (deg) 107231(2)
γ (deg) 90
V (Aring3) 23664(2)
Z 4
T (K) 150(2)
ρcalcd (gcm3) 1378
μ (mmndash1) 0952
Reflections collected 57791
Significant reflections 9306
R[I gt 25 (I)] 00450
Rw[I gt 25 (I)] 00999
Goodness of fit 07317
Table S2 Selected bond lengths of CuIILAPIP
Bond LAPIPCuII
Cu(1)-N(2) 1955 (1958)
Cu(1)-N(3) 1955 (1972)
Cu(1)-N(4) 1921 (1924)
Cu(1)-O(5) 1901 (1895)
C(17)-O(5) 1322 (1326)
C(22)-N(4) 1414 (1412)
C(23)-N(4) 1284 (1297)
C(6)-N(2) 1400 (1400)
C(6)-O(2) 1230 (1230)
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Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
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Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
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Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S2
Content
Materials and Physical Methods
S3
Material Synthesis
S3
Figure S1 LC-MS spectrum of HLIPIP
S4
Figure S2 ESI-MS(HRMS) spectrum of CuLIPIP
S6
Figure S3 Molecular structure of CuIILIPIP S6
Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2
18O
S7
Figure S5 1H NMR of NiLAPIP-OH
S7
Figure S6 13 C NMR of NiLAPIP-OH
S8
Figure S7 ESI-MS(HRMS) spectrum of NiLAPIP-OH
S8
Figure S8 1H NMR of NiLAPIP crystals compare with NiLAPIP-OH
S9
Figure S9 EPR silent spectrum of NiIILAPIP
S10
Figure S10 Molecular structure of NiIILAPIP-MeO
S10
Figure S11 1H NMR of NiIILAPIP-MeO
S11
Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP
S11
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
S12
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan rate 200 mV s CH2Cl2 298 K
S12
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fc
S12
X-Ray Crystallography data of Copper Zinc and Nickel complexes
S13
S3
Materials and Physical Methods All reagents and solvents were purchased from commercial sources and were used as received unless noted otherwise Anhydrous Cu(OAc)2 98 Super dry acetonitrile dichloromethane were used for synthesis and growing crystal as mentioned Preparation and handling of air- and moisture-sensitive materials were carried out under an inert gas atmosphere of glove box NMR spectra were recorded at 400 MHz on a Bruker DRX spectrometer in CDCl3 solution The chemical shifts were referred to TMS using the residual signals from the solvent IR spectra were recorded in the solid state on a FT-IR Bruker Vector 22 spectrophotometer in the 400minus4000 cm-1 range LC-MS mass spectral data were acquired on Shimadzu LCMS 2020 HRMS spectra were recorded on thermo Fisher scientific LTQ Orbitrap Elite Cyclic Voltammetry (CV) was performed on CHI605E CH Instruments USA equipped with a Ag wire reference electrode a glassy carbon working electrode and a Pt counter electrode with 01 M Bu4N(BF4) solutions in CH2Cl2 Ferrocene was used as an internal standard
X-ray Crystallographic Analyses All crystals were placed onto the tip of a 01 mm diameter glass capillary and mounted on a Bruker SMART Platform CCD diffractometer for data collection The data collections were carried out using MoKαradiation with a graphite monochromator (λ= 071073 A) at 95 K Structure solutions were performed by direct methods using SHELXS-97 software and refined against F2using full-matrix-least-squares using SHELXL-97 and SHELXL-2013 software Data intensities were corrected for absorption and decay (SADABS) Final cell constants were obtained from least squares fits of all measured reflections All non-hydrogen atoms were refined with anisotropic displacement parameters
Material Synthesis To a solution of 35-DTBQ (35-di-tert-butylcyclohexa-35-diene-12-dione) (022 g 1 mmol) in acetonitrile (4 mL) was added 2-aminobenzyl amine (0122 g 1 mmol) and the reaction solution stirred for 30 min at the room temperature in the presence of air After some minutes it afforded a yellow precipitate (scheme S1) 1H NMR (400 MHz Chloroform-d) δ 870 (s 1H) 746 (dd 1H) 728 (dt 2H) 705 (d 1H) 679 (m 2H) 671 (s 1H) 627 (s 2H) 151 (s 9H) 140 (s 9H)
Scheme S1 Synthesis of HLAP ligand
Next to the stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1
mmol) (Scheme S2) LC-MS data clearly shows the formation of this ligand (Figure S1)
This ligand (HLIPIP) is stable at dry and inert condition When it is exposed on moisture it is hydrolyzed Therefore after one
minute stirring different metal precursors of copper zinc and nickel were added to reaction mixture to afford the metal
complexes (Scheme S3)
Scheme S2 Synthesis of HLIPIP ligand
S4
Figure S1 LC-MS spectrum of HLIPIP
Scheme 3 General scheme for the preparation of the different metal complexes
S5
Synthesis of CuIILAPIP
CuIILAPIP complex was synthesized by the following template reaction Firstly to the stirred suspension of HLAP (0324 g 1 mmol)
in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) after one minute stirring Cu(OAc)2H2O (0199 g 1
mmol) was added in the presence of 2 equivalents of NEt3 to the reaction mixture
The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate of copper complex The filtrate was left
undisturbed to afford red brown microcrystals (0309 g 63 yield) by evaporation from dichloromethaneacetonitrile solution
X-ray quality dark red single crystals were grown from a 11 solvent mixture of n-hexanedichloromethane Elemental Analysis
calculated (found) for C27H29N3O2Cu035 C6H14 C 6705 H 655 N 806 Found C 6679 H 661 N 776 νmax(KBr)cm-1 2959 (C-
H) 1642(C=O) 1466 (C=N) 802 (=C-H bending) ESI-MS mz 4912
Synthesis of CuIILIPIP
CuIILIPIP complex was synthesized by the following template reaction Firstly to a stirred suspension of HLAP (0324 g 1 mmol) in
dry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) Next Cu(OAc)2 (0181 g 1 mmol) was added to the
reaction mixture The stirring of orange-brown solution at 298 K for 4 h afforded a dark orange precipitate of copper complex
X-ray quality dark red single crystals from were grown from dry acetonitriledichloromethane ESI-MS mz ()4761751
Synthesis of CuIILAPIP-Meo
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
After one minute stirring Cu (OAc)2H2O (0199 g 1 mmol) was added in the presence of 2 equivalents of NEt3 to the reaction
mixture The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate X-ray quality dark red single
crystals were grown from a 11 solvent mixture of methanoldichloromethane
Synthesis of ZnLIPIPOAc As reported to a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1
mmol) After one minute stirring it was reacted immediately with Zn (OAc)2 2H2O (0219 g 1 mmol) to afford the zinc complex
of ZnIILIPIPOAc at the ambient temperature The stirring of black solution at 298 K for 4 h afforded a dark red-brown precipitate
X-ray quality dark crystals were grown from methanol
νmax(KBr)cm-1 3415 (OndashH) 2946 (CndashH) 1606 (C=O) 1593 (C=C) 1469 (C=N) 740 (=CndashH bending) 1H NMR (400 MHz (CD3)2SO) δ 129 (s 9H) 145 (s 9H) 159 (s 3H) 71 (d 1H) 74 (d 1H) 76 (m 2H) 78 (dd 1H) 80 (m
1H) 82 (d 1H) 84 (dt 9Hz 1H) 89 (m1H) 90(s 1H) 91(s 1H) 13C NMR (100 MHz (CD3)2SO) δ 2982 3000 3213 3221 3442 3553 10979 12103 12455 12899 12922 12963
12974 13200 13237 13354 135511385314190 145061474414999153081611716271
Synthesis of NiIILAPIP-OH
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
under N2 atmosphere (Figure S1) After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to
afford the nickel complex of NiIILAPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded
a precipitate ESI-MS mz ()4881843 1H NMR (400 MHz DMSO-d6) δ 880 (s 1H) 860 (dt J = 531 146 Hz 1H) 810 (td J = 769 157 Hz 1H) 777 (dd J = 741 184 Hz 2H) 764 (dd J = 761 522 Hz 2H) 737 (d J = 891 Hz 1H) 724 (ddd J = 873 663 174 Hz 1H) 696 (d J = 209 Hz 1H) 660 (ddd J = 775 660 097 Hz 1H) 634 (d J = 1012 Hz 1H) 607 (d J = 1006 Hz 1H) 145 (s 9H) 133 (s 9H) 13C NMR (101 MHz DMSO) δ 2976 3242 3460 3487 8840 11002 11387 11686 12066 12092 12491 13149 13454 14014 14114 14624 14821 14908 16014 16657
Synthesis of NiIILAPIP Solvent slow evaporation of NiLAPIP-OH solution from dichloromethaneacetonitrile afforded single crystal of NiIILAPIP ESI-MS mz
()4861880
Synthesis of NiIILIPIP
To a stirred suspension of HLAP (0324 g 1 mmol) in superdry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1
mmol) under N2 atmosphere After one minute stirring it was reacted immediately with Ni(OAc)2 (1 mmol 0176 g) to afford
the nickel complex of NiIILIPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded a
precipitate ESI-MS mz ()4711808
S6
Synthesis of NiIILAPIP-MeO
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to afford the nickel complex at the ambient temperature The stirring of dark orange solution at 298 K for 4 h afforded a precipitate X-ray quality dark crystals were grown from dichloromethanemethanol 1H NMR (400 MHz DMSO-d6) δ 885 (s 1H) 864 (ddd J = 560 154 074 Hz 1H) 817 (td J = 767 156 Hz 1H) 787 ndash 777 (m 2H) 777 ndash 765 (m 2H) 738 (d J = 884 Hz 1H) 728 (ddd J = 873 666 176 Hz 1H) 698 (d J = 206 Hz 1H) 667 (ddd J = 786 670 101 Hz 1H) 630 (s 1H) 301 (s 3H) 145 (s 9H) 133 (s 9H)
Figures and Tables
Figure S2 ESI-MS (HRMS) spectrum of CuLIPIP
Figure S3 Molecular structure of CuIILIPIP Hydrogen atoms have been omitted for clarity Thermal ellipsoids are set at 50 probability Acetonitrile molecule with the occupancy set to 50 was also found in the structure
BCL-Z5 72 RT 048 AV 1 NL 145E3T FTMS + p ESI Full ms [5000-100000]
4759 4760 4761 4762 4763 4764 4765 4766 4767
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4761751
S7
200 300 400 500 600 700 800
0
20
40
60
80
100
Rel
ativ
e In
tens
ity
mz
49345
Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2
18O
Figure S5 1H NMR of NiLAPIP- OH
S8
Figure S6 13 C NMR of NiLAPIP-OH
Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH
BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]
4877 4878 4879 4880 4881 4882 4883 4884 4885 4886
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4881843
S9
Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)
(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to
amide)
S10
Figure S9 EPR silent spectrum of NiIILAPIP
Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are
set at 50 probability
-100000
-80000
-60000
-40000
-20000
0
20000
40000
60000
80000
100000
2500 3000 3500 4000 4500
S11
Figure S11 1H NMR of NiIILAPIP-MeO
Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP
BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]
4706 4708 4710 4712 4714 4716 4718
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4711808
S12
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
compound E121 V E12
2 V
CuIILAPIP +041 -166
NiIILAPIP +051 -181
ZnIILIPIPOAc +027 -147
aPeak to peak difference for the Fc+ Fc couple at 298 K is 012
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan
rate 200 mV s CH2Cl2 298 K
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca
compound V112E V2
12E
CuIILIPIP +021 -160
NiIILIPIP +032
-189
-25 -2 -15 -1 -05 0 05 1
S13
X-Ray Crystallography data of Copper Zinc and nickel complexes
Table S1 Crystallographic data for CuIILAPIP
CuIILAPIP
Empirical formula C27 H29 Cu N3 O2
Formula weight 49109
Crystal system Monoclinic
Space group P1 21c 1
a (Aring) 95598(5)
b (Aring) 182903(9)
c (Aring) 141699(8)
α (deg) 90
β (deg) 107231(2)
γ (deg) 90
V (Aring3) 23664(2)
Z 4
T (K) 150(2)
ρcalcd (gcm3) 1378
μ (mmndash1) 0952
Reflections collected 57791
Significant reflections 9306
R[I gt 25 (I)] 00450
Rw[I gt 25 (I)] 00999
Goodness of fit 07317
Table S2 Selected bond lengths of CuIILAPIP
Bond LAPIPCuII
Cu(1)-N(2) 1955 (1958)
Cu(1)-N(3) 1955 (1972)
Cu(1)-N(4) 1921 (1924)
Cu(1)-O(5) 1901 (1895)
C(17)-O(5) 1322 (1326)
C(22)-N(4) 1414 (1412)
C(23)-N(4) 1284 (1297)
C(6)-N(2) 1400 (1400)
C(6)-O(2) 1230 (1230)
S14
Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S3
Materials and Physical Methods All reagents and solvents were purchased from commercial sources and were used as received unless noted otherwise Anhydrous Cu(OAc)2 98 Super dry acetonitrile dichloromethane were used for synthesis and growing crystal as mentioned Preparation and handling of air- and moisture-sensitive materials were carried out under an inert gas atmosphere of glove box NMR spectra were recorded at 400 MHz on a Bruker DRX spectrometer in CDCl3 solution The chemical shifts were referred to TMS using the residual signals from the solvent IR spectra were recorded in the solid state on a FT-IR Bruker Vector 22 spectrophotometer in the 400minus4000 cm-1 range LC-MS mass spectral data were acquired on Shimadzu LCMS 2020 HRMS spectra were recorded on thermo Fisher scientific LTQ Orbitrap Elite Cyclic Voltammetry (CV) was performed on CHI605E CH Instruments USA equipped with a Ag wire reference electrode a glassy carbon working electrode and a Pt counter electrode with 01 M Bu4N(BF4) solutions in CH2Cl2 Ferrocene was used as an internal standard
X-ray Crystallographic Analyses All crystals were placed onto the tip of a 01 mm diameter glass capillary and mounted on a Bruker SMART Platform CCD diffractometer for data collection The data collections were carried out using MoKαradiation with a graphite monochromator (λ= 071073 A) at 95 K Structure solutions were performed by direct methods using SHELXS-97 software and refined against F2using full-matrix-least-squares using SHELXL-97 and SHELXL-2013 software Data intensities were corrected for absorption and decay (SADABS) Final cell constants were obtained from least squares fits of all measured reflections All non-hydrogen atoms were refined with anisotropic displacement parameters
Material Synthesis To a solution of 35-DTBQ (35-di-tert-butylcyclohexa-35-diene-12-dione) (022 g 1 mmol) in acetonitrile (4 mL) was added 2-aminobenzyl amine (0122 g 1 mmol) and the reaction solution stirred for 30 min at the room temperature in the presence of air After some minutes it afforded a yellow precipitate (scheme S1) 1H NMR (400 MHz Chloroform-d) δ 870 (s 1H) 746 (dd 1H) 728 (dt 2H) 705 (d 1H) 679 (m 2H) 671 (s 1H) 627 (s 2H) 151 (s 9H) 140 (s 9H)
Scheme S1 Synthesis of HLAP ligand
Next to the stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1
mmol) (Scheme S2) LC-MS data clearly shows the formation of this ligand (Figure S1)
This ligand (HLIPIP) is stable at dry and inert condition When it is exposed on moisture it is hydrolyzed Therefore after one
minute stirring different metal precursors of copper zinc and nickel were added to reaction mixture to afford the metal
complexes (Scheme S3)
Scheme S2 Synthesis of HLIPIP ligand
S4
Figure S1 LC-MS spectrum of HLIPIP
Scheme 3 General scheme for the preparation of the different metal complexes
S5
Synthesis of CuIILAPIP
CuIILAPIP complex was synthesized by the following template reaction Firstly to the stirred suspension of HLAP (0324 g 1 mmol)
in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) after one minute stirring Cu(OAc)2H2O (0199 g 1
mmol) was added in the presence of 2 equivalents of NEt3 to the reaction mixture
The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate of copper complex The filtrate was left
undisturbed to afford red brown microcrystals (0309 g 63 yield) by evaporation from dichloromethaneacetonitrile solution
X-ray quality dark red single crystals were grown from a 11 solvent mixture of n-hexanedichloromethane Elemental Analysis
calculated (found) for C27H29N3O2Cu035 C6H14 C 6705 H 655 N 806 Found C 6679 H 661 N 776 νmax(KBr)cm-1 2959 (C-
H) 1642(C=O) 1466 (C=N) 802 (=C-H bending) ESI-MS mz 4912
Synthesis of CuIILIPIP
CuIILIPIP complex was synthesized by the following template reaction Firstly to a stirred suspension of HLAP (0324 g 1 mmol) in
dry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) Next Cu(OAc)2 (0181 g 1 mmol) was added to the
reaction mixture The stirring of orange-brown solution at 298 K for 4 h afforded a dark orange precipitate of copper complex
X-ray quality dark red single crystals from were grown from dry acetonitriledichloromethane ESI-MS mz ()4761751
Synthesis of CuIILAPIP-Meo
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
After one minute stirring Cu (OAc)2H2O (0199 g 1 mmol) was added in the presence of 2 equivalents of NEt3 to the reaction
mixture The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate X-ray quality dark red single
crystals were grown from a 11 solvent mixture of methanoldichloromethane
Synthesis of ZnLIPIPOAc As reported to a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1
mmol) After one minute stirring it was reacted immediately with Zn (OAc)2 2H2O (0219 g 1 mmol) to afford the zinc complex
of ZnIILIPIPOAc at the ambient temperature The stirring of black solution at 298 K for 4 h afforded a dark red-brown precipitate
X-ray quality dark crystals were grown from methanol
νmax(KBr)cm-1 3415 (OndashH) 2946 (CndashH) 1606 (C=O) 1593 (C=C) 1469 (C=N) 740 (=CndashH bending) 1H NMR (400 MHz (CD3)2SO) δ 129 (s 9H) 145 (s 9H) 159 (s 3H) 71 (d 1H) 74 (d 1H) 76 (m 2H) 78 (dd 1H) 80 (m
1H) 82 (d 1H) 84 (dt 9Hz 1H) 89 (m1H) 90(s 1H) 91(s 1H) 13C NMR (100 MHz (CD3)2SO) δ 2982 3000 3213 3221 3442 3553 10979 12103 12455 12899 12922 12963
12974 13200 13237 13354 135511385314190 145061474414999153081611716271
Synthesis of NiIILAPIP-OH
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
under N2 atmosphere (Figure S1) After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to
afford the nickel complex of NiIILAPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded
a precipitate ESI-MS mz ()4881843 1H NMR (400 MHz DMSO-d6) δ 880 (s 1H) 860 (dt J = 531 146 Hz 1H) 810 (td J = 769 157 Hz 1H) 777 (dd J = 741 184 Hz 2H) 764 (dd J = 761 522 Hz 2H) 737 (d J = 891 Hz 1H) 724 (ddd J = 873 663 174 Hz 1H) 696 (d J = 209 Hz 1H) 660 (ddd J = 775 660 097 Hz 1H) 634 (d J = 1012 Hz 1H) 607 (d J = 1006 Hz 1H) 145 (s 9H) 133 (s 9H) 13C NMR (101 MHz DMSO) δ 2976 3242 3460 3487 8840 11002 11387 11686 12066 12092 12491 13149 13454 14014 14114 14624 14821 14908 16014 16657
Synthesis of NiIILAPIP Solvent slow evaporation of NiLAPIP-OH solution from dichloromethaneacetonitrile afforded single crystal of NiIILAPIP ESI-MS mz
()4861880
Synthesis of NiIILIPIP
To a stirred suspension of HLAP (0324 g 1 mmol) in superdry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1
mmol) under N2 atmosphere After one minute stirring it was reacted immediately with Ni(OAc)2 (1 mmol 0176 g) to afford
the nickel complex of NiIILIPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded a
precipitate ESI-MS mz ()4711808
S6
Synthesis of NiIILAPIP-MeO
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to afford the nickel complex at the ambient temperature The stirring of dark orange solution at 298 K for 4 h afforded a precipitate X-ray quality dark crystals were grown from dichloromethanemethanol 1H NMR (400 MHz DMSO-d6) δ 885 (s 1H) 864 (ddd J = 560 154 074 Hz 1H) 817 (td J = 767 156 Hz 1H) 787 ndash 777 (m 2H) 777 ndash 765 (m 2H) 738 (d J = 884 Hz 1H) 728 (ddd J = 873 666 176 Hz 1H) 698 (d J = 206 Hz 1H) 667 (ddd J = 786 670 101 Hz 1H) 630 (s 1H) 301 (s 3H) 145 (s 9H) 133 (s 9H)
Figures and Tables
Figure S2 ESI-MS (HRMS) spectrum of CuLIPIP
Figure S3 Molecular structure of CuIILIPIP Hydrogen atoms have been omitted for clarity Thermal ellipsoids are set at 50 probability Acetonitrile molecule with the occupancy set to 50 was also found in the structure
BCL-Z5 72 RT 048 AV 1 NL 145E3T FTMS + p ESI Full ms [5000-100000]
4759 4760 4761 4762 4763 4764 4765 4766 4767
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4761751
S7
200 300 400 500 600 700 800
0
20
40
60
80
100
Rel
ativ
e In
tens
ity
mz
49345
Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2
18O
Figure S5 1H NMR of NiLAPIP- OH
S8
Figure S6 13 C NMR of NiLAPIP-OH
Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH
BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]
4877 4878 4879 4880 4881 4882 4883 4884 4885 4886
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4881843
S9
Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)
(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to
amide)
S10
Figure S9 EPR silent spectrum of NiIILAPIP
Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are
set at 50 probability
-100000
-80000
-60000
-40000
-20000
0
20000
40000
60000
80000
100000
2500 3000 3500 4000 4500
S11
Figure S11 1H NMR of NiIILAPIP-MeO
Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP
BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]
4706 4708 4710 4712 4714 4716 4718
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4711808
S12
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
compound E121 V E12
2 V
CuIILAPIP +041 -166
NiIILAPIP +051 -181
ZnIILIPIPOAc +027 -147
aPeak to peak difference for the Fc+ Fc couple at 298 K is 012
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan
rate 200 mV s CH2Cl2 298 K
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca
compound V112E V2
12E
CuIILIPIP +021 -160
NiIILIPIP +032
-189
-25 -2 -15 -1 -05 0 05 1
S13
X-Ray Crystallography data of Copper Zinc and nickel complexes
Table S1 Crystallographic data for CuIILAPIP
CuIILAPIP
Empirical formula C27 H29 Cu N3 O2
Formula weight 49109
Crystal system Monoclinic
Space group P1 21c 1
a (Aring) 95598(5)
b (Aring) 182903(9)
c (Aring) 141699(8)
α (deg) 90
β (deg) 107231(2)
γ (deg) 90
V (Aring3) 23664(2)
Z 4
T (K) 150(2)
ρcalcd (gcm3) 1378
μ (mmndash1) 0952
Reflections collected 57791
Significant reflections 9306
R[I gt 25 (I)] 00450
Rw[I gt 25 (I)] 00999
Goodness of fit 07317
Table S2 Selected bond lengths of CuIILAPIP
Bond LAPIPCuII
Cu(1)-N(2) 1955 (1958)
Cu(1)-N(3) 1955 (1972)
Cu(1)-N(4) 1921 (1924)
Cu(1)-O(5) 1901 (1895)
C(17)-O(5) 1322 (1326)
C(22)-N(4) 1414 (1412)
C(23)-N(4) 1284 (1297)
C(6)-N(2) 1400 (1400)
C(6)-O(2) 1230 (1230)
S14
Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S4
Figure S1 LC-MS spectrum of HLIPIP
Scheme 3 General scheme for the preparation of the different metal complexes
S5
Synthesis of CuIILAPIP
CuIILAPIP complex was synthesized by the following template reaction Firstly to the stirred suspension of HLAP (0324 g 1 mmol)
in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) after one minute stirring Cu(OAc)2H2O (0199 g 1
mmol) was added in the presence of 2 equivalents of NEt3 to the reaction mixture
The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate of copper complex The filtrate was left
undisturbed to afford red brown microcrystals (0309 g 63 yield) by evaporation from dichloromethaneacetonitrile solution
X-ray quality dark red single crystals were grown from a 11 solvent mixture of n-hexanedichloromethane Elemental Analysis
calculated (found) for C27H29N3O2Cu035 C6H14 C 6705 H 655 N 806 Found C 6679 H 661 N 776 νmax(KBr)cm-1 2959 (C-
H) 1642(C=O) 1466 (C=N) 802 (=C-H bending) ESI-MS mz 4912
Synthesis of CuIILIPIP
CuIILIPIP complex was synthesized by the following template reaction Firstly to a stirred suspension of HLAP (0324 g 1 mmol) in
dry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) Next Cu(OAc)2 (0181 g 1 mmol) was added to the
reaction mixture The stirring of orange-brown solution at 298 K for 4 h afforded a dark orange precipitate of copper complex
X-ray quality dark red single crystals from were grown from dry acetonitriledichloromethane ESI-MS mz ()4761751
Synthesis of CuIILAPIP-Meo
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
After one minute stirring Cu (OAc)2H2O (0199 g 1 mmol) was added in the presence of 2 equivalents of NEt3 to the reaction
mixture The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate X-ray quality dark red single
crystals were grown from a 11 solvent mixture of methanoldichloromethane
Synthesis of ZnLIPIPOAc As reported to a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1
mmol) After one minute stirring it was reacted immediately with Zn (OAc)2 2H2O (0219 g 1 mmol) to afford the zinc complex
of ZnIILIPIPOAc at the ambient temperature The stirring of black solution at 298 K for 4 h afforded a dark red-brown precipitate
X-ray quality dark crystals were grown from methanol
νmax(KBr)cm-1 3415 (OndashH) 2946 (CndashH) 1606 (C=O) 1593 (C=C) 1469 (C=N) 740 (=CndashH bending) 1H NMR (400 MHz (CD3)2SO) δ 129 (s 9H) 145 (s 9H) 159 (s 3H) 71 (d 1H) 74 (d 1H) 76 (m 2H) 78 (dd 1H) 80 (m
1H) 82 (d 1H) 84 (dt 9Hz 1H) 89 (m1H) 90(s 1H) 91(s 1H) 13C NMR (100 MHz (CD3)2SO) δ 2982 3000 3213 3221 3442 3553 10979 12103 12455 12899 12922 12963
12974 13200 13237 13354 135511385314190 145061474414999153081611716271
Synthesis of NiIILAPIP-OH
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
under N2 atmosphere (Figure S1) After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to
afford the nickel complex of NiIILAPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded
a precipitate ESI-MS mz ()4881843 1H NMR (400 MHz DMSO-d6) δ 880 (s 1H) 860 (dt J = 531 146 Hz 1H) 810 (td J = 769 157 Hz 1H) 777 (dd J = 741 184 Hz 2H) 764 (dd J = 761 522 Hz 2H) 737 (d J = 891 Hz 1H) 724 (ddd J = 873 663 174 Hz 1H) 696 (d J = 209 Hz 1H) 660 (ddd J = 775 660 097 Hz 1H) 634 (d J = 1012 Hz 1H) 607 (d J = 1006 Hz 1H) 145 (s 9H) 133 (s 9H) 13C NMR (101 MHz DMSO) δ 2976 3242 3460 3487 8840 11002 11387 11686 12066 12092 12491 13149 13454 14014 14114 14624 14821 14908 16014 16657
Synthesis of NiIILAPIP Solvent slow evaporation of NiLAPIP-OH solution from dichloromethaneacetonitrile afforded single crystal of NiIILAPIP ESI-MS mz
()4861880
Synthesis of NiIILIPIP
To a stirred suspension of HLAP (0324 g 1 mmol) in superdry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1
mmol) under N2 atmosphere After one minute stirring it was reacted immediately with Ni(OAc)2 (1 mmol 0176 g) to afford
the nickel complex of NiIILIPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded a
precipitate ESI-MS mz ()4711808
S6
Synthesis of NiIILAPIP-MeO
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to afford the nickel complex at the ambient temperature The stirring of dark orange solution at 298 K for 4 h afforded a precipitate X-ray quality dark crystals were grown from dichloromethanemethanol 1H NMR (400 MHz DMSO-d6) δ 885 (s 1H) 864 (ddd J = 560 154 074 Hz 1H) 817 (td J = 767 156 Hz 1H) 787 ndash 777 (m 2H) 777 ndash 765 (m 2H) 738 (d J = 884 Hz 1H) 728 (ddd J = 873 666 176 Hz 1H) 698 (d J = 206 Hz 1H) 667 (ddd J = 786 670 101 Hz 1H) 630 (s 1H) 301 (s 3H) 145 (s 9H) 133 (s 9H)
Figures and Tables
Figure S2 ESI-MS (HRMS) spectrum of CuLIPIP
Figure S3 Molecular structure of CuIILIPIP Hydrogen atoms have been omitted for clarity Thermal ellipsoids are set at 50 probability Acetonitrile molecule with the occupancy set to 50 was also found in the structure
BCL-Z5 72 RT 048 AV 1 NL 145E3T FTMS + p ESI Full ms [5000-100000]
4759 4760 4761 4762 4763 4764 4765 4766 4767
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4761751
S7
200 300 400 500 600 700 800
0
20
40
60
80
100
Rel
ativ
e In
tens
ity
mz
49345
Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2
18O
Figure S5 1H NMR of NiLAPIP- OH
S8
Figure S6 13 C NMR of NiLAPIP-OH
Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH
BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]
4877 4878 4879 4880 4881 4882 4883 4884 4885 4886
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4881843
S9
Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)
(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to
amide)
S10
Figure S9 EPR silent spectrum of NiIILAPIP
Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are
set at 50 probability
-100000
-80000
-60000
-40000
-20000
0
20000
40000
60000
80000
100000
2500 3000 3500 4000 4500
S11
Figure S11 1H NMR of NiIILAPIP-MeO
Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP
BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]
4706 4708 4710 4712 4714 4716 4718
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4711808
S12
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
compound E121 V E12
2 V
CuIILAPIP +041 -166
NiIILAPIP +051 -181
ZnIILIPIPOAc +027 -147
aPeak to peak difference for the Fc+ Fc couple at 298 K is 012
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan
rate 200 mV s CH2Cl2 298 K
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca
compound V112E V2
12E
CuIILIPIP +021 -160
NiIILIPIP +032
-189
-25 -2 -15 -1 -05 0 05 1
S13
X-Ray Crystallography data of Copper Zinc and nickel complexes
Table S1 Crystallographic data for CuIILAPIP
CuIILAPIP
Empirical formula C27 H29 Cu N3 O2
Formula weight 49109
Crystal system Monoclinic
Space group P1 21c 1
a (Aring) 95598(5)
b (Aring) 182903(9)
c (Aring) 141699(8)
α (deg) 90
β (deg) 107231(2)
γ (deg) 90
V (Aring3) 23664(2)
Z 4
T (K) 150(2)
ρcalcd (gcm3) 1378
μ (mmndash1) 0952
Reflections collected 57791
Significant reflections 9306
R[I gt 25 (I)] 00450
Rw[I gt 25 (I)] 00999
Goodness of fit 07317
Table S2 Selected bond lengths of CuIILAPIP
Bond LAPIPCuII
Cu(1)-N(2) 1955 (1958)
Cu(1)-N(3) 1955 (1972)
Cu(1)-N(4) 1921 (1924)
Cu(1)-O(5) 1901 (1895)
C(17)-O(5) 1322 (1326)
C(22)-N(4) 1414 (1412)
C(23)-N(4) 1284 (1297)
C(6)-N(2) 1400 (1400)
C(6)-O(2) 1230 (1230)
S14
Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S5
Synthesis of CuIILAPIP
CuIILAPIP complex was synthesized by the following template reaction Firstly to the stirred suspension of HLAP (0324 g 1 mmol)
in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) after one minute stirring Cu(OAc)2H2O (0199 g 1
mmol) was added in the presence of 2 equivalents of NEt3 to the reaction mixture
The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate of copper complex The filtrate was left
undisturbed to afford red brown microcrystals (0309 g 63 yield) by evaporation from dichloromethaneacetonitrile solution
X-ray quality dark red single crystals were grown from a 11 solvent mixture of n-hexanedichloromethane Elemental Analysis
calculated (found) for C27H29N3O2Cu035 C6H14 C 6705 H 655 N 806 Found C 6679 H 661 N 776 νmax(KBr)cm-1 2959 (C-
H) 1642(C=O) 1466 (C=N) 802 (=C-H bending) ESI-MS mz 4912
Synthesis of CuIILIPIP
CuIILIPIP complex was synthesized by the following template reaction Firstly to a stirred suspension of HLAP (0324 g 1 mmol) in
dry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol) Next Cu(OAc)2 (0181 g 1 mmol) was added to the
reaction mixture The stirring of orange-brown solution at 298 K for 4 h afforded a dark orange precipitate of copper complex
X-ray quality dark red single crystals from were grown from dry acetonitriledichloromethane ESI-MS mz ()4761751
Synthesis of CuIILAPIP-Meo
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
After one minute stirring Cu (OAc)2H2O (0199 g 1 mmol) was added in the presence of 2 equivalents of NEt3 to the reaction
mixture The stirring of red-brown solution at 298 K for 4 h afforded a red-brown precipitate X-ray quality dark red single
crystals were grown from a 11 solvent mixture of methanoldichloromethane
Synthesis of ZnLIPIPOAc As reported to a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1
mmol) After one minute stirring it was reacted immediately with Zn (OAc)2 2H2O (0219 g 1 mmol) to afford the zinc complex
of ZnIILIPIPOAc at the ambient temperature The stirring of black solution at 298 K for 4 h afforded a dark red-brown precipitate
X-ray quality dark crystals were grown from methanol
νmax(KBr)cm-1 3415 (OndashH) 2946 (CndashH) 1606 (C=O) 1593 (C=C) 1469 (C=N) 740 (=CndashH bending) 1H NMR (400 MHz (CD3)2SO) δ 129 (s 9H) 145 (s 9H) 159 (s 3H) 71 (d 1H) 74 (d 1H) 76 (m 2H) 78 (dd 1H) 80 (m
1H) 82 (d 1H) 84 (dt 9Hz 1H) 89 (m1H) 90(s 1H) 91(s 1H) 13C NMR (100 MHz (CD3)2SO) δ 2982 3000 3213 3221 3442 3553 10979 12103 12455 12899 12922 12963
12974 13200 13237 13354 135511385314190 145061474414999153081611716271
Synthesis of NiIILAPIP-OH
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
under N2 atmosphere (Figure S1) After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to
afford the nickel complex of NiIILAPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded
a precipitate ESI-MS mz ()4881843 1H NMR (400 MHz DMSO-d6) δ 880 (s 1H) 860 (dt J = 531 146 Hz 1H) 810 (td J = 769 157 Hz 1H) 777 (dd J = 741 184 Hz 2H) 764 (dd J = 761 522 Hz 2H) 737 (d J = 891 Hz 1H) 724 (ddd J = 873 663 174 Hz 1H) 696 (d J = 209 Hz 1H) 660 (ddd J = 775 660 097 Hz 1H) 634 (d J = 1012 Hz 1H) 607 (d J = 1006 Hz 1H) 145 (s 9H) 133 (s 9H) 13C NMR (101 MHz DMSO) δ 2976 3242 3460 3487 8840 11002 11387 11686 12066 12092 12491 13149 13454 14014 14114 14624 14821 14908 16014 16657
Synthesis of NiIILAPIP Solvent slow evaporation of NiLAPIP-OH solution from dichloromethaneacetonitrile afforded single crystal of NiIILAPIP ESI-MS mz
()4861880
Synthesis of NiIILIPIP
To a stirred suspension of HLAP (0324 g 1 mmol) in superdry acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1
mmol) under N2 atmosphere After one minute stirring it was reacted immediately with Ni(OAc)2 (1 mmol 0176 g) to afford
the nickel complex of NiIILIPIP at the ambient temperature The stirring of dark orange solution at 298 K for 2 h afforded a
precipitate ESI-MS mz ()4711808
S6
Synthesis of NiIILAPIP-MeO
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to afford the nickel complex at the ambient temperature The stirring of dark orange solution at 298 K for 4 h afforded a precipitate X-ray quality dark crystals were grown from dichloromethanemethanol 1H NMR (400 MHz DMSO-d6) δ 885 (s 1H) 864 (ddd J = 560 154 074 Hz 1H) 817 (td J = 767 156 Hz 1H) 787 ndash 777 (m 2H) 777 ndash 765 (m 2H) 738 (d J = 884 Hz 1H) 728 (ddd J = 873 666 176 Hz 1H) 698 (d J = 206 Hz 1H) 667 (ddd J = 786 670 101 Hz 1H) 630 (s 1H) 301 (s 3H) 145 (s 9H) 133 (s 9H)
Figures and Tables
Figure S2 ESI-MS (HRMS) spectrum of CuLIPIP
Figure S3 Molecular structure of CuIILIPIP Hydrogen atoms have been omitted for clarity Thermal ellipsoids are set at 50 probability Acetonitrile molecule with the occupancy set to 50 was also found in the structure
BCL-Z5 72 RT 048 AV 1 NL 145E3T FTMS + p ESI Full ms [5000-100000]
4759 4760 4761 4762 4763 4764 4765 4766 4767
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4761751
S7
200 300 400 500 600 700 800
0
20
40
60
80
100
Rel
ativ
e In
tens
ity
mz
49345
Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2
18O
Figure S5 1H NMR of NiLAPIP- OH
S8
Figure S6 13 C NMR of NiLAPIP-OH
Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH
BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]
4877 4878 4879 4880 4881 4882 4883 4884 4885 4886
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4881843
S9
Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)
(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to
amide)
S10
Figure S9 EPR silent spectrum of NiIILAPIP
Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are
set at 50 probability
-100000
-80000
-60000
-40000
-20000
0
20000
40000
60000
80000
100000
2500 3000 3500 4000 4500
S11
Figure S11 1H NMR of NiIILAPIP-MeO
Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP
BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]
4706 4708 4710 4712 4714 4716 4718
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4711808
S12
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
compound E121 V E12
2 V
CuIILAPIP +041 -166
NiIILAPIP +051 -181
ZnIILIPIPOAc +027 -147
aPeak to peak difference for the Fc+ Fc couple at 298 K is 012
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan
rate 200 mV s CH2Cl2 298 K
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca
compound V112E V2
12E
CuIILIPIP +021 -160
NiIILIPIP +032
-189
-25 -2 -15 -1 -05 0 05 1
S13
X-Ray Crystallography data of Copper Zinc and nickel complexes
Table S1 Crystallographic data for CuIILAPIP
CuIILAPIP
Empirical formula C27 H29 Cu N3 O2
Formula weight 49109
Crystal system Monoclinic
Space group P1 21c 1
a (Aring) 95598(5)
b (Aring) 182903(9)
c (Aring) 141699(8)
α (deg) 90
β (deg) 107231(2)
γ (deg) 90
V (Aring3) 23664(2)
Z 4
T (K) 150(2)
ρcalcd (gcm3) 1378
μ (mmndash1) 0952
Reflections collected 57791
Significant reflections 9306
R[I gt 25 (I)] 00450
Rw[I gt 25 (I)] 00999
Goodness of fit 07317
Table S2 Selected bond lengths of CuIILAPIP
Bond LAPIPCuII
Cu(1)-N(2) 1955 (1958)
Cu(1)-N(3) 1955 (1972)
Cu(1)-N(4) 1921 (1924)
Cu(1)-O(5) 1901 (1895)
C(17)-O(5) 1322 (1326)
C(22)-N(4) 1414 (1412)
C(23)-N(4) 1284 (1297)
C(6)-N(2) 1400 (1400)
C(6)-O(2) 1230 (1230)
S14
Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S6
Synthesis of NiIILAPIP-MeO
To a stirred suspension of HLAP (0324 g 1 mmol) in acetonitrile was added pyridine-2-carboxaldehyde (0096 mL 1 mmol)
After one minute stirring it was reacted immediately with Ni(OAc)24H2O (1 mmol 0248 g) to afford the nickel complex at the ambient temperature The stirring of dark orange solution at 298 K for 4 h afforded a precipitate X-ray quality dark crystals were grown from dichloromethanemethanol 1H NMR (400 MHz DMSO-d6) δ 885 (s 1H) 864 (ddd J = 560 154 074 Hz 1H) 817 (td J = 767 156 Hz 1H) 787 ndash 777 (m 2H) 777 ndash 765 (m 2H) 738 (d J = 884 Hz 1H) 728 (ddd J = 873 666 176 Hz 1H) 698 (d J = 206 Hz 1H) 667 (ddd J = 786 670 101 Hz 1H) 630 (s 1H) 301 (s 3H) 145 (s 9H) 133 (s 9H)
Figures and Tables
Figure S2 ESI-MS (HRMS) spectrum of CuLIPIP
Figure S3 Molecular structure of CuIILIPIP Hydrogen atoms have been omitted for clarity Thermal ellipsoids are set at 50 probability Acetonitrile molecule with the occupancy set to 50 was also found in the structure
BCL-Z5 72 RT 048 AV 1 NL 145E3T FTMS + p ESI Full ms [5000-100000]
4759 4760 4761 4762 4763 4764 4765 4766 4767
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4761751
S7
200 300 400 500 600 700 800
0
20
40
60
80
100
Rel
ativ
e In
tens
ity
mz
49345
Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2
18O
Figure S5 1H NMR of NiLAPIP- OH
S8
Figure S6 13 C NMR of NiLAPIP-OH
Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH
BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]
4877 4878 4879 4880 4881 4882 4883 4884 4885 4886
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4881843
S9
Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)
(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to
amide)
S10
Figure S9 EPR silent spectrum of NiIILAPIP
Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are
set at 50 probability
-100000
-80000
-60000
-40000
-20000
0
20000
40000
60000
80000
100000
2500 3000 3500 4000 4500
S11
Figure S11 1H NMR of NiIILAPIP-MeO
Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP
BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]
4706 4708 4710 4712 4714 4716 4718
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4711808
S12
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
compound E121 V E12
2 V
CuIILAPIP +041 -166
NiIILAPIP +051 -181
ZnIILIPIPOAc +027 -147
aPeak to peak difference for the Fc+ Fc couple at 298 K is 012
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan
rate 200 mV s CH2Cl2 298 K
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca
compound V112E V2
12E
CuIILIPIP +021 -160
NiIILIPIP +032
-189
-25 -2 -15 -1 -05 0 05 1
S13
X-Ray Crystallography data of Copper Zinc and nickel complexes
Table S1 Crystallographic data for CuIILAPIP
CuIILAPIP
Empirical formula C27 H29 Cu N3 O2
Formula weight 49109
Crystal system Monoclinic
Space group P1 21c 1
a (Aring) 95598(5)
b (Aring) 182903(9)
c (Aring) 141699(8)
α (deg) 90
β (deg) 107231(2)
γ (deg) 90
V (Aring3) 23664(2)
Z 4
T (K) 150(2)
ρcalcd (gcm3) 1378
μ (mmndash1) 0952
Reflections collected 57791
Significant reflections 9306
R[I gt 25 (I)] 00450
Rw[I gt 25 (I)] 00999
Goodness of fit 07317
Table S2 Selected bond lengths of CuIILAPIP
Bond LAPIPCuII
Cu(1)-N(2) 1955 (1958)
Cu(1)-N(3) 1955 (1972)
Cu(1)-N(4) 1921 (1924)
Cu(1)-O(5) 1901 (1895)
C(17)-O(5) 1322 (1326)
C(22)-N(4) 1414 (1412)
C(23)-N(4) 1284 (1297)
C(6)-N(2) 1400 (1400)
C(6)-O(2) 1230 (1230)
S14
Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S7
200 300 400 500 600 700 800
0
20
40
60
80
100
Rel
ativ
e In
tens
ity
mz
49345
Figure S4 Isotope experiment of the reactions aminophenol-iminopyridine ligand and Cu(OAc)2 in the presence of H2
18O
Figure S5 1H NMR of NiLAPIP- OH
S8
Figure S6 13 C NMR of NiLAPIP-OH
Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH
BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]
4877 4878 4879 4880 4881 4882 4883 4884 4885 4886
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4881843
S9
Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)
(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to
amide)
S10
Figure S9 EPR silent spectrum of NiIILAPIP
Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are
set at 50 probability
-100000
-80000
-60000
-40000
-20000
0
20000
40000
60000
80000
100000
2500 3000 3500 4000 4500
S11
Figure S11 1H NMR of NiIILAPIP-MeO
Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP
BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]
4706 4708 4710 4712 4714 4716 4718
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4711808
S12
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
compound E121 V E12
2 V
CuIILAPIP +041 -166
NiIILAPIP +051 -181
ZnIILIPIPOAc +027 -147
aPeak to peak difference for the Fc+ Fc couple at 298 K is 012
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan
rate 200 mV s CH2Cl2 298 K
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca
compound V112E V2
12E
CuIILIPIP +021 -160
NiIILIPIP +032
-189
-25 -2 -15 -1 -05 0 05 1
S13
X-Ray Crystallography data of Copper Zinc and nickel complexes
Table S1 Crystallographic data for CuIILAPIP
CuIILAPIP
Empirical formula C27 H29 Cu N3 O2
Formula weight 49109
Crystal system Monoclinic
Space group P1 21c 1
a (Aring) 95598(5)
b (Aring) 182903(9)
c (Aring) 141699(8)
α (deg) 90
β (deg) 107231(2)
γ (deg) 90
V (Aring3) 23664(2)
Z 4
T (K) 150(2)
ρcalcd (gcm3) 1378
μ (mmndash1) 0952
Reflections collected 57791
Significant reflections 9306
R[I gt 25 (I)] 00450
Rw[I gt 25 (I)] 00999
Goodness of fit 07317
Table S2 Selected bond lengths of CuIILAPIP
Bond LAPIPCuII
Cu(1)-N(2) 1955 (1958)
Cu(1)-N(3) 1955 (1972)
Cu(1)-N(4) 1921 (1924)
Cu(1)-O(5) 1901 (1895)
C(17)-O(5) 1322 (1326)
C(22)-N(4) 1414 (1412)
C(23)-N(4) 1284 (1297)
C(6)-N(2) 1400 (1400)
C(6)-O(2) 1230 (1230)
S14
Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S8
Figure S6 13 C NMR of NiLAPIP-OH
Figure S7 ESI-MS (HRMS) spectrum of NiLAPIP-OH
BCL-Z3 41 RT 028 AV 1 NL 772E2T FTMS + p ESI Full ms [5000-100000]
4877 4878 4879 4880 4881 4882 4883 4884 4885 4886
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4881843
S9
Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)
(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to
amide)
S10
Figure S9 EPR silent spectrum of NiIILAPIP
Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are
set at 50 probability
-100000
-80000
-60000
-40000
-20000
0
20000
40000
60000
80000
100000
2500 3000 3500 4000 4500
S11
Figure S11 1H NMR of NiIILAPIP-MeO
Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP
BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]
4706 4708 4710 4712 4714 4716 4718
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4711808
S12
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
compound E121 V E12
2 V
CuIILAPIP +041 -166
NiIILAPIP +051 -181
ZnIILIPIPOAc +027 -147
aPeak to peak difference for the Fc+ Fc couple at 298 K is 012
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan
rate 200 mV s CH2Cl2 298 K
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca
compound V112E V2
12E
CuIILIPIP +021 -160
NiIILIPIP +032
-189
-25 -2 -15 -1 -05 0 05 1
S13
X-Ray Crystallography data of Copper Zinc and nickel complexes
Table S1 Crystallographic data for CuIILAPIP
CuIILAPIP
Empirical formula C27 H29 Cu N3 O2
Formula weight 49109
Crystal system Monoclinic
Space group P1 21c 1
a (Aring) 95598(5)
b (Aring) 182903(9)
c (Aring) 141699(8)
α (deg) 90
β (deg) 107231(2)
γ (deg) 90
V (Aring3) 23664(2)
Z 4
T (K) 150(2)
ρcalcd (gcm3) 1378
μ (mmndash1) 0952
Reflections collected 57791
Significant reflections 9306
R[I gt 25 (I)] 00450
Rw[I gt 25 (I)] 00999
Goodness of fit 07317
Table S2 Selected bond lengths of CuIILAPIP
Bond LAPIPCuII
Cu(1)-N(2) 1955 (1958)
Cu(1)-N(3) 1955 (1972)
Cu(1)-N(4) 1921 (1924)
Cu(1)-O(5) 1901 (1895)
C(17)-O(5) 1322 (1326)
C(22)-N(4) 1414 (1412)
C(23)-N(4) 1284 (1297)
C(6)-N(2) 1400 (1400)
C(6)-O(2) 1230 (1230)
S14
Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S9
Figure S8 1H NMR of NiLAPIP crystals (top) compare with NiLAPIP-OH (down)
(There is a small amount of NiLAPIP-OH impurity in NiLAPIP crystals revealing gradually oxidation of imine moiety to
amide)
S10
Figure S9 EPR silent spectrum of NiIILAPIP
Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are
set at 50 probability
-100000
-80000
-60000
-40000
-20000
0
20000
40000
60000
80000
100000
2500 3000 3500 4000 4500
S11
Figure S11 1H NMR of NiIILAPIP-MeO
Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP
BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]
4706 4708 4710 4712 4714 4716 4718
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4711808
S12
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
compound E121 V E12
2 V
CuIILAPIP +041 -166
NiIILAPIP +051 -181
ZnIILIPIPOAc +027 -147
aPeak to peak difference for the Fc+ Fc couple at 298 K is 012
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan
rate 200 mV s CH2Cl2 298 K
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca
compound V112E V2
12E
CuIILIPIP +021 -160
NiIILIPIP +032
-189
-25 -2 -15 -1 -05 0 05 1
S13
X-Ray Crystallography data of Copper Zinc and nickel complexes
Table S1 Crystallographic data for CuIILAPIP
CuIILAPIP
Empirical formula C27 H29 Cu N3 O2
Formula weight 49109
Crystal system Monoclinic
Space group P1 21c 1
a (Aring) 95598(5)
b (Aring) 182903(9)
c (Aring) 141699(8)
α (deg) 90
β (deg) 107231(2)
γ (deg) 90
V (Aring3) 23664(2)
Z 4
T (K) 150(2)
ρcalcd (gcm3) 1378
μ (mmndash1) 0952
Reflections collected 57791
Significant reflections 9306
R[I gt 25 (I)] 00450
Rw[I gt 25 (I)] 00999
Goodness of fit 07317
Table S2 Selected bond lengths of CuIILAPIP
Bond LAPIPCuII
Cu(1)-N(2) 1955 (1958)
Cu(1)-N(3) 1955 (1972)
Cu(1)-N(4) 1921 (1924)
Cu(1)-O(5) 1901 (1895)
C(17)-O(5) 1322 (1326)
C(22)-N(4) 1414 (1412)
C(23)-N(4) 1284 (1297)
C(6)-N(2) 1400 (1400)
C(6)-O(2) 1230 (1230)
S14
Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S10
Figure S9 EPR silent spectrum of NiIILAPIP
Figure S10 Molecular structure of NiIILAPIP-OMeHydrogen atoms have been omitted for clarity Thermal ellipsoids are
set at 50 probability
-100000
-80000
-60000
-40000
-20000
0
20000
40000
60000
80000
100000
2500 3000 3500 4000 4500
S11
Figure S11 1H NMR of NiIILAPIP-MeO
Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP
BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]
4706 4708 4710 4712 4714 4716 4718
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4711808
S12
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
compound E121 V E12
2 V
CuIILAPIP +041 -166
NiIILAPIP +051 -181
ZnIILIPIPOAc +027 -147
aPeak to peak difference for the Fc+ Fc couple at 298 K is 012
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan
rate 200 mV s CH2Cl2 298 K
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca
compound V112E V2
12E
CuIILIPIP +021 -160
NiIILIPIP +032
-189
-25 -2 -15 -1 -05 0 05 1
S13
X-Ray Crystallography data of Copper Zinc and nickel complexes
Table S1 Crystallographic data for CuIILAPIP
CuIILAPIP
Empirical formula C27 H29 Cu N3 O2
Formula weight 49109
Crystal system Monoclinic
Space group P1 21c 1
a (Aring) 95598(5)
b (Aring) 182903(9)
c (Aring) 141699(8)
α (deg) 90
β (deg) 107231(2)
γ (deg) 90
V (Aring3) 23664(2)
Z 4
T (K) 150(2)
ρcalcd (gcm3) 1378
μ (mmndash1) 0952
Reflections collected 57791
Significant reflections 9306
R[I gt 25 (I)] 00450
Rw[I gt 25 (I)] 00999
Goodness of fit 07317
Table S2 Selected bond lengths of CuIILAPIP
Bond LAPIPCuII
Cu(1)-N(2) 1955 (1958)
Cu(1)-N(3) 1955 (1972)
Cu(1)-N(4) 1921 (1924)
Cu(1)-O(5) 1901 (1895)
C(17)-O(5) 1322 (1326)
C(22)-N(4) 1414 (1412)
C(23)-N(4) 1284 (1297)
C(6)-N(2) 1400 (1400)
C(6)-O(2) 1230 (1230)
S14
Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S11
Figure S11 1H NMR of NiIILAPIP-MeO
Figure S12 ESI-MS (HRMS) spectrum of NiLIPIP
BCL-Z1 20 RT 018 AV 1 NL 163E3T FTMS + p ESI Full ms [5000-100000]
4706 4708 4710 4712 4714 4716 4718
mz
0
10
20
30
40
50
60
70
80
90
100
Re
lative
Ab
un
da
nce
4711808
S12
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
compound E121 V E12
2 V
CuIILAPIP +041 -166
NiIILAPIP +051 -181
ZnIILIPIPOAc +027 -147
aPeak to peak difference for the Fc+ Fc couple at 298 K is 012
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan
rate 200 mV s CH2Cl2 298 K
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca
compound V112E V2
12E
CuIILIPIP +021 -160
NiIILIPIP +032
-189
-25 -2 -15 -1 -05 0 05 1
S13
X-Ray Crystallography data of Copper Zinc and nickel complexes
Table S1 Crystallographic data for CuIILAPIP
CuIILAPIP
Empirical formula C27 H29 Cu N3 O2
Formula weight 49109
Crystal system Monoclinic
Space group P1 21c 1
a (Aring) 95598(5)
b (Aring) 182903(9)
c (Aring) 141699(8)
α (deg) 90
β (deg) 107231(2)
γ (deg) 90
V (Aring3) 23664(2)
Z 4
T (K) 150(2)
ρcalcd (gcm3) 1378
μ (mmndash1) 0952
Reflections collected 57791
Significant reflections 9306
R[I gt 25 (I)] 00450
Rw[I gt 25 (I)] 00999
Goodness of fit 07317
Table S2 Selected bond lengths of CuIILAPIP
Bond LAPIPCuII
Cu(1)-N(2) 1955 (1958)
Cu(1)-N(3) 1955 (1972)
Cu(1)-N(4) 1921 (1924)
Cu(1)-O(5) 1901 (1895)
C(17)-O(5) 1322 (1326)
C(22)-N(4) 1414 (1412)
C(23)-N(4) 1284 (1297)
C(6)-N(2) 1400 (1400)
C(6)-O(2) 1230 (1230)
S14
Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S12
Table S1 Redox potentials of cyclic voltammogram of CuIILAPIP NiIILAPIP and ZnIILIPIPOAc versus Fc+ Fca
compound E121 V E12
2 V
CuIILAPIP +041 -166
NiIILAPIP +051 -181
ZnIILIPIPOAc +027 -147
aPeak to peak difference for the Fc+ Fc couple at 298 K is 012
Figure S13 Cyclic voltammogram of CuIILIPIP (Red) NiIILIPIP (Blue) Conditions 25 mM complex 01 M NBu4(BF4) scan
rate 200 mV s CH2Cl2 298 K
Table S2 Redox potentials of cyclic voltammogram of CuIILIPIP and NiIILIPIP versus Fc+ Fca
compound V112E V2
12E
CuIILIPIP +021 -160
NiIILIPIP +032
-189
-25 -2 -15 -1 -05 0 05 1
S13
X-Ray Crystallography data of Copper Zinc and nickel complexes
Table S1 Crystallographic data for CuIILAPIP
CuIILAPIP
Empirical formula C27 H29 Cu N3 O2
Formula weight 49109
Crystal system Monoclinic
Space group P1 21c 1
a (Aring) 95598(5)
b (Aring) 182903(9)
c (Aring) 141699(8)
α (deg) 90
β (deg) 107231(2)
γ (deg) 90
V (Aring3) 23664(2)
Z 4
T (K) 150(2)
ρcalcd (gcm3) 1378
μ (mmndash1) 0952
Reflections collected 57791
Significant reflections 9306
R[I gt 25 (I)] 00450
Rw[I gt 25 (I)] 00999
Goodness of fit 07317
Table S2 Selected bond lengths of CuIILAPIP
Bond LAPIPCuII
Cu(1)-N(2) 1955 (1958)
Cu(1)-N(3) 1955 (1972)
Cu(1)-N(4) 1921 (1924)
Cu(1)-O(5) 1901 (1895)
C(17)-O(5) 1322 (1326)
C(22)-N(4) 1414 (1412)
C(23)-N(4) 1284 (1297)
C(6)-N(2) 1400 (1400)
C(6)-O(2) 1230 (1230)
S14
Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S13
X-Ray Crystallography data of Copper Zinc and nickel complexes
Table S1 Crystallographic data for CuIILAPIP
CuIILAPIP
Empirical formula C27 H29 Cu N3 O2
Formula weight 49109
Crystal system Monoclinic
Space group P1 21c 1
a (Aring) 95598(5)
b (Aring) 182903(9)
c (Aring) 141699(8)
α (deg) 90
β (deg) 107231(2)
γ (deg) 90
V (Aring3) 23664(2)
Z 4
T (K) 150(2)
ρcalcd (gcm3) 1378
μ (mmndash1) 0952
Reflections collected 57791
Significant reflections 9306
R[I gt 25 (I)] 00450
Rw[I gt 25 (I)] 00999
Goodness of fit 07317
Table S2 Selected bond lengths of CuIILAPIP
Bond LAPIPCuII
Cu(1)-N(2) 1955 (1958)
Cu(1)-N(3) 1955 (1972)
Cu(1)-N(4) 1921 (1924)
Cu(1)-O(5) 1901 (1895)
C(17)-O(5) 1322 (1326)
C(22)-N(4) 1414 (1412)
C(23)-N(4) 1284 (1297)
C(6)-N(2) 1400 (1400)
C(6)-O(2) 1230 (1230)
S14
Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S14
Table S3 Crystallographic data for CuIILIPIP
Table S4 Selected bond lengths of CuIILIPIP
Number Atom1 Atom2 Length
1 Cu1 N1 1965
2 Cu1 O1 1912
3 Cu1 N2 1903
4 Cu1 N3 1928
5 H1 C1 101
6 N1 C1 1343
7 N1 C5 1322
8 O1 C19 1331
9 C1 C2 1372
10 C2 H2 082
11 C2 C3 137
12 N2 C7 1366
13 N2 C6 144
14 C3 H3 085
15 C3 C4 1385
16 N3 C13 1298
17 N3 C14 1417
18 C4 H4 0995
LIPIPCuII
Empirical formula C29 H33 Cu N4 O
Formula weight 51714
Crystal system Orthorhombic
Space group Pnma
a (Aring) 24983(3)
b (Aring) 69452(7)
c (Aring) 163797(17)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 28421
Z 4
T (K) 296
ρcalcd (gcm3) 1209
μ (mmndash1) 0794
Significant reflections 6328
R[I gt 25 (I)] 00561
Rw[I gt 25 (I)] 01637
Goodness of fit 0997
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S15
Table S5 Crystallographic data for CuIILAPIP-MeO
Table S6 Selected bond lengths of CuIILAPIP-MeO
Number Atom1 Atom2 Length
1 Cu1 N1 1963(2)
2 Cu1 N2 1911(2)
3 Cu1 N3 1919(2)
4 Cu1 O1 1902(2)
5 N1 C5 1333(3)
6 N1 C1 1339(4)
7 N2 C6 1429(4)
8 N2 C7 1368(3)
9 N3 C14 1423(3)
10 N3 C13 1293(3)
11 O1 C19 1320(3)
12 C4 C5 1379(4)
13 C4 C3 1367(5)
14 C4 H4 088(3)
15 C5 C6 1508(4)
16 C6 H6 109(2)
17 C6 O2 1451(3)
18 C1 C2 1368(4)
19 C1 H1 091(3)
20 C2 C3 1366(5)
CuIILAPIP-MeO
Empirical formula C28 H33 Cu N3 O2
Formula weight 50712
Crystal system Orthorhombic
Space group Pbca
a (Aring) 158660(8)
b (Aring) 145267(7)
c (Aring) 220264(11)
α (deg) 9000
β (deg) 9000
γ (deg) 9000
V (Aring3) 507666
Z 8
T (K) 296
ρcalcd (gcm3) 1327
μ (mmndash1) 0890
Significant reflections 6328
R[I gt 25 (I)] 00470
Rw[I gt 25 (I)] 01261
Goodness of fit 0997
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S16
21 C2 H2 085(3)
22 C3 H3 086(3)
23 C19 C14 1407(4)
24 C19 C18 1418(4)
25 C14 C15 1391(4)
26 C18 C17 1382(4)
27 C18 C20 1538(4)
28 C16 C15 1378(4)
29 C16 C17 1396(4)
30 C16 C24 1537(4)
31 C13 C12 1433(4)
32 C13 H13 092(3)
33 C15 H15 089(2)
34 C12 C7 1426(4)
35 C12 C11 1409(4)
36 C7 C8 1419(4)
37 C11 C10 1362(5)
38 C11 H11 089(3)
39 C17 H17 093(3)
Table S7 Crystallographic data for ZnLAPIPOAc
ZnIILAPIPOAc
Empirical formula C29 H34 N3 O350 Zn
Formula weight 54596
Temperature K 293(2)
Wavelength Aring 071073
Crystal system space group Triclinic P-1
Unit cell dimensions Aringdeg a = 101927(13)
b = 102059(12)
c = 147907(19)
alpha = 94834(10)
beta = 98779(11)
gamma = 114583(12)
Volume Aring3 13640(3)
Z Calculated density Mgm3 2 1329
Absorption coefficient mm-1 0937
Goodness-of-fit on F2 1073
Final R indices [Igt2sigma(I)] R1 = 00631 wR2 = 01711
R indices (all data) R1 = 00871 wR2 = 02184
Largest diff peak and hole eAring-3 0891 and -0568
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S17
Table S8 Bond lengths of ZnLIPIPOAc
Bond length
Angles
Zn1-O1 1978(3) O1-Zn1-O2 11195(14)
Zn1-O2 1991(4) O1-Zn1-N1 8173(12)
Zn1-N1 2087(3) O2-Zn1-N1 11706(15)
Zn1-N3 2109(4) O1-Zn1-N3 9671(13)
Zn1-N2 2174(3) O2-Zn1-N3 10545(15)
O1-C1 1311(5) N1-Zn1-N3 13479(14)
C1-C2 1431(5) O1-Zn1-N2 15335(14)
C1-C6 1432(5) O2-Zn1-N2 9467(13)
C2-C3 1392(5) N1-Zn1-N2 8504(13)
C2-C20 1543(5) N3-Zn1-N2 7660(13)
C3-C4 1391(6) C1-O1-Zn1 1147(2)
C4-C5 1390(6) O1-C1-C2 1230(3)
C4-C24 1546(6) O1-C1-C6 1198(3)
C5-C6 1386(5) C2-C1-C6 1171(3)
C6-N1 1426(5) C3-C2-C1 1191(3)
N1-C7 1281(5) C3-C2-C20 1213(4)
C7-C8 1471(6) C1-C2-C20 1196(3)
C8-C9 1394(6) C4-C3-C2 1235(4)
C8-C13 1428(6) C5-C4-C3 1175(4)
C9-C10 1390(6) C5-C4-C24 1215(4)
C10-C11 1364(7) C3-C4-C24 1211(4)
C11-C12 1383(7) C6-C5-C4 1218(4)
C12-C13 1394(6) C5-C6-N1 1252(4)
C13-N2 1419(5) C5-C6-C1 1211(4)
N2-C14 1249(6) N1-C6-C1 1136(3)
C14-C15 1465(6) C7-N1-C6 1235(3)
C15-N3 1354(6) C7-N1-Zn1 1262(3)
C15-C16 1374(6) C6-N1-Zn1 1101(2)
C16-C17 1389(7) N1-C7-C8 1272(4)
C17-C18 1400(8) C9-C8-C13 1168(4)
C18-C19 1380(7) C9-C8-C7 1165(4)
C19-N3 1326(6) C13-C8-C7 1267(4)
C20-C21 1528(7) C10-C9-C8 1217(4)
C20-C23 1531(7) C11-C10-C9 1209(4)
C20-C22 1552(6) C10-C11-C12 1197(4)
C24-C27 1493(9) C11-C12-C13 1206(4)
C24-C25 1502(7) C12-C13-N2 1218(4)
C24-C26 1569(8) C12-C13-C8 1204(4)
O2-C28 1209(7) N2-C13-C8 1178(4)
C28-O3 1246(7) C14-N2-C13 1216(4)
C28-C29 1528(9) C14-N2-Zn1 1143(3)
C13-N2-Zn1 1240(3)
N2-C14-C15 1189(4)
N3-C15-C16 1225(4)
N3-C15-C14 1155(4)
C16-C15-C14 1219(4)
C15-C16-C17 1186(5)
C16-C17-C18 1187(5)
C19-C18-C17 1191(5)
N3-C19-C18 1220(5)
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S18
Table S9 Crystallographic data for NiIILAPIP
Table S10 Selected bond lengths of NiIILAPIP
Atom1 Atom2 Length
Ni1 N1 1846(2)
Ni1 O1 1838(2)
Ni1 N2 1885(2)
Ni1 N3 1888(2)
N1 C13 1287(4)
N1 C14 1417(3)
O1 C19 1333(2)
C1 C2 1378(4)
C1 N2 1329(4)
C2 H2 0929(3)
C2 C3 1378(4)
O2 C6 1224(3)
N2 C5 1342(3)
C3 H3 0929(3)
C3 C4 1379(4)
N3 C6 1379(3)
N3 C7 1393(4)
C5 C6 1487(4)
C5 C4 1380(4)
C7 C8 1410(4)
C7 C12 1412(4)
NiIILAPIP
Empirical formula C27 H29 Ni N3 O2
Formula weight 48622
Crystal system Monoclinic
Space group P 21c
a (Aring) 97052(6)
b (Aring) 180704(11)
c (Aring) 141301(10)
α (deg) 90
β (deg) 1078527(15)
γ (deg) 90
V (Aring3) 235877
Z 4
T (K) 296
ρcalcd (gcm3) 1369
μ (mmndash1) 0852
R[I gt 25 (I)] 004361
Rw[I gt 25 (I)] 01353
Goodness of fit 07317
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S19
Table S11 Crystallographic data for for monoclinic form of NiIILAPIP-MeO
NiIILAPIP-MeO
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Crystal system Monoclinic
Space group P 21c
a (Aring) 115267(8) A
b (Aring) 166156(10) A
c (Aring) 136845(9)
α (deg) 90
β (deg) 104524(7)
γ (deg) 90
V (Aring3) 25371(3)
Z 4
T (K) 298
ρcalcd (gcm3) 1315
R[I gt 25 (I)] R1 = 00339
Rw[I gt 25 (I)] wR2 = 00869
Goodness of fit 1073
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S20
Table S12 Selected bond lengths for monoclinic form of NiIILAPIP-MeO
Number Atom1 Atom2 Length
1 Ni1 O1 1843(2)
2 Ni1 N1 1844(2)
3 Ni1 N2 1852(2)
4 Ni1 N3 1882(2)
5 O1 C1 1331(4)
6 C1 C2 1413(4)
7 C1 C6 1408(4)
8 C2 C3 1385(4)
9 C2 C20 1537(5)
10 C3 H3A 093
11 C3 C4 1409(4)
12 C4 C5 1386(4)
13 C4 C24 1538(4)
14 C5 H5A 093
15 C5 C6 1396(4)
16 C6 N1 1425(3)
17 N1 C7 1308(4)
19 C7 C8 1420(4)
20 C8 C9 1417(4)
21 C8 C13 1431(4)
23 C9 C10 1360(4)
25 C10 C11 1400(5)
27 C11 C12 1376(5)
29 C12 C13 1418(4)
30 C13 N2 1367(4)
31 N2 C14 1448(4)
33 C14 C15 1504(4)
34 C14 O2 1438(3)
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S21
Table S13 Crystallographic data for triclinic form of NiIILAPIP-MeO
Identification code NiIILAPIP-MeO e712a
Empirical formula C28 H33 N3 Ni O2
Formula weight 50228
Temperature 293(2) K
Wavelength 071073 Aring
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 93643(8) Aring
b = 99780(8) Aring
c = 143688(12) Aring
α = 101276(7)deg
β = 95203(7)deg
γ = 99728(7)deg
Volume 128704(19) Aring3
Z 2
Density (calculated) 1296 Mgm3
Absorption coefficient 0783 mm-1
F(000) 532
Crystal size 0544 x 0318 x 0130 mm3
Theta range for data collection 2225 to 28096deg
Index ranges -6lt=hlt=12 -12lt=klt=11 -17lt=llt=18
Reflections collected 8310
Independent reflections 5514 [R(int) = 00542]
Completeness to theta = 25000deg 999
Absorption correction Analytical
Max and min transmission 0909 and 0725
Refinement method Full-matrix least-squares on F2
Data restraints parameters 5514 0 307
Goodness-of-fit on F2 1028
Final R indices [Igt2sigma(I)] R1 = 00470 wR2 = 01246
R indices (all data) R1 = 00671 wR2 = 01377
Extinction coefficient na
Largest diff peak and hole 0408 and -0517 eAring-3
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
S23
S22
Table S14 Selected bond lengths for triclinic form of NiIILAPIP-MeO
Bond Angle
Ni1-O1 18431(18) O1-Ni1-N1 8658(8)
Ni1-N1 1844(2) O1-Ni1-N2 17597(9)
Ni1-N2 1853(2) N1-Ni1-N2 9636(9)
Ni1-N3 1881(2) O1-Ni1-N3 9135(9)
O1-C1 1330(3) N1-Ni1-N3 17769(9)
C1-C6 1408(3) N2-Ni1-N3 8577(9)
C1-C2 1413(3) C1-O1-Ni1 11308(16)
C2-C3 1386(4) O1-C1-C6 1168(2)
C2-C20 1537(4) O1-C1-C2 1242(2)
C3-C4 1409(4) C6-C1-C2 1190(2)
C4-C5 1385(3) C3-C2-C1 1169(2)
C4-C24 1539(3) C3-C2-C20 1227(2)
C5-C6 1395(3) C1-C2-C20 1204(2)
C6-N1 1425(3) C2-C3-C4 1247(2)
N1-C7 1308(3) C5-C4-C3 1174(2)
C7-C8 1422(3) C5-C4-C24 1233(2)
C8-C9 1418(4) C3-C4-C24 1193(2)
C8-C13 1429(4) C4-C5-C6 1197(2)
C9-C10 1360(4) C5-C6-C1 1221(2)
C10-C11 1401(4) C5-C6-N1 1267(2)
C10-H10A 09300 C1-C6-N1 1112(2)
C11-C12 1376(4) C7-N1-C6 1219(2)
C12-C13 1418(3) C7-N1-Ni1 12588(18)
C13-N2 1367(3) C6-N1-Ni1 11219(16)
N2-C14 1448(3) N1-C7-C8 1255(2)
C14-O2 1437(3) C9-C8-C7 1165(2)
C14-C15 1505(4) C9-C8-C13 1195(2)
C15-N3 1346(3) C7-C8-C13 1239(2)
C15-C16 1381(4) C10-C9-C8 1226(3)
C16-C17 1378(5) C9-C10-C11 1179(3)
C17-C18 1389(5) C12-C11-C10 1217(3)
C18-C19 1366(4) C11-C12-C13 1217(3)
C19-N3 1349(4) N2-C13-C12 1228(2)
C20-C23 1520(5) N2-C13-C8 1207(2)
C20-C21 1530(4) C12-C13-C8 1165(2)
C20-C22 1534(5) C13-N2-C14 1170(2)
C24-C27 1521(4) C13-N2-Ni1 12727(18)
C24-C26 1524(4) C14-N2-Ni1 11536(18)
C24-C25 1529(4) O2-C14-N2 1150(2)
O2-C28 1405(4) O2-C14-C15 1092(2)
N2-C14-C15 1088(2)
N3-C15-C16 1219(3)
N3-C15-C14 1149(2)
C16-C15-C14 1231(3)
C17-C16-C15 1194(3)
C16-C17-C18 1187(3)
C19-C18-C17 1191(3)
N3-C19-C18 1226(3)
C15-N3-C19 1183(3)
C15-N3-Ni1 11497(19)
C19-N3-Ni1 1268(2)
C23-C20-C21 1079(3)
C23-C20-C22 1094(3)
C21-C20-C22 1084(3)
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