of gni*cin'lf, --{(* lli; li · 367 makalah pendamping kimia si{-i3fs il 13 maret 2010 paralel...
TRANSCRIPT
367 Makalah PendamPing Kimia SI{-I3FS il 13 Maret 2010Paralel F
STRUCTURALANDMAGNETICPRoPERTIESoTC00RDINATIoNP0LYMERlfe(prc)rllliCr(oxhl
Fahimah Martakl, Di ulia onggor, Ismunandart, Agung Nugroho2, Ibrahim Baba3'
Nandang Mufti*
llnorganic and Physical Chemistry Group' ITB' Indonesia
Email : fahima-riza@Yahoo'com
2 physics of lvtagn*ir* uidTh6iiri"E-*iarch Group, ITB, Indonesia
: S"toofoiCfr'emi"al Sciences and Technology, UKM, Malaysia
+ i*iilnstitute of Advanced Materials, RuG, The Netherlands
AbstractA polymer complex with formula of [Fe(pic)5]iLic.(o*)rl _tn-1c
: picolinic acid, ox=oxalate) has been
prepared from direct ,;i." ;i sotution'or'iii"i*ri. @iI) tet ugoorouorate and tris(oxalate) lithium
chromate(IlD under nitrogen atmospher€- characterization ofthe complex was made by microanalyses' FT-
IR spectroscop,, x-ray iimu.tion- and magpetometer. The polymei structur€ of the complex has been
determined and refined using Le Bail method,'it "tyt"ffi*t in a cubic structure ylttr yace group of P213'
a:,5.2840(18) andf-+. fiemagnetic properties of the complex has been studied in the temperature range
between 5 to 300 r. rne .f*.tiri moment "i;J u, *a c*i" weiss temperature of 7 '13 K are obtained
from correlation between magnetic susceptibilifr u!tt* ,.rperatur' This indicates that the complex has a
ferromagnetic interaction and suggests tfr" -ud"ti" mo-""t'a'" dominated by ion iron(ID in the high spin
state.
Keywords: complex polymer, crystal structure' ferromagtetic interaction
ii
IntroductionThe field of research based on
molecule-based magnets has e*p"T!:n-c*
remarkable growth in the past decade --" lt ts
"o* well--recognized that coordination
compounds are ldeal building blocks. for a,rtiity of solid state materials including
noom temperature magnets' One of most
fertite *"* in molecular magnetism is
transition-metals oxalato complexes'. a
"*r.qu"n.e of the fact that the oxalato
bridge promotes magnetic coupling between
paramagnetic metal centers'r-'- Ifrolecular based magnet with formula
AM0M([I)(Czoq)r] (A:--5.: --{(*c,n)of,' gNi*cin'lf, [N(n-c5H11)a]*'
fPt Crn lli; M(IIF Mn" Fe' Cu' Co' Zn
Li r"r: f", ct has been ieported u-'o' These
crmpoonds have shown to behave as ferro or
ferrimagnet properties with critical
temperatures ranging from 6- ty . aa K'
Int"t*ot"",rlar intiractions in the bimetallic
compounds are in general very-weak.and as
,".oit tU" critical timperature, Tc, is limited
to low temperature. Thereby, the idea oftransition-mital complex insertion on the
1U'U1ox;31'- building block is a reasonably
synthesis strateg1l-
The use of tris(bipyridil) complex
cation, tz([)(bpy[]2. ( Z(D = Fe, Co, Ni'n"l n, fvriUp<C<m)(ox)31- havg led to the
fo.rnutioo ' of three-dimensional network
iZiiiltupvXltM(tr)c(c(tu)(9x):ltclo4l, it
;;;6;tda by coronado"' These three-
dimensional compound behave also as ferro
*J t"tti*agnet but with lower ordering
temperatur -than their two-dimensional
analogues. However, Sieber .and Hauserl2
[p"tt"O that [Co(bpy) d2* which normally
high spin ground state when
irlotpotut"d in the oxalate network'
{tco(bpv) rlll-(DCr(Illxoxhl}, becomes a
spin crossover system.
In the Present PaPer the PolYmeric
complex that obtained by - combining the
**rl"* cation [Fe(picolinic)3]'* with the
ii<inXo*l l'- and t i(aq) is presented'
fn" pt*p*"tion, structural characterization
*a Lugn"tic study of the compound of
formula- [Fe{picolinic)3]tli(I)C(mXox):lhas reported.
2. ExPeriment2.l Matcrials
All chemicals were of reagent grade
and were used as commeroially obtained'
368 Makalah Pend:rmping Kimia
Standard literature proceduresl3 wereysed to prepare the staring materialsKs [Cr(CzO+):].3F{zO, A&[C(CuOa)3].2H2O.
2.2 fnstrumentsMetal content was determined by
Absorpfion Atomic Spectroscopy ShimadzuAA8801S. Elemental analyses (C, H, N)were performed on Fison EA I l0gmicroanalytical analyzer at UniversityKebangsaan Malaysia. The FT-IR spectrawas recorded on Shimadzu FTIR_g400spectrometer in the 4000 - 400 cm'r spectralregions. Powder x-ray diffractionmeasurements was performed philips pW1835 Difractometer using Cu Ko radiation, atAustralian National Beamline, Japan.Magnetic susceptibility measurements( 5-300 K ) were carried out using a euantumDesign MPMSR-2 5T SeUID magnetometer(measurements carried out at 1000 Oe)performed at Groningen University, TheNederlands.
2.3 Synthesis of [Fe(pic)31 [LiCr(ox)31Polymeric Complex
Complexes of [Fe(pic)3][BFa]2 andAgr[C(ox)3] were prepared to used asprecursor to produce [Fe(pic)3][LiC(oxhJ.
Synthesis of [Fe(pic)3|[BFnlz complexTo a solution of Fe(BFa)2.6HzO (0.34
g, I mmol) in 3 mL methanol, a hot solutionof picolinic acid (0.39 g,3.21mmol ) in 10mL of methanol was added. The reactionmixture was heated at 70-80 oC under Nz gasfor 30 min. A red precipitate appeared wasfiltered out, and dried over paoro.
Synthesis of Ag[Cr(ox)31 complexTo an aqueous solution of
K3[C(ox)3].3HzO (0.a9 g I mmol) in 5 mLof water, a solution of AgNO3 (0.51 gram, 3mmol) in 5 mL of water was added. Thereaction mixture was stirred for 30 min underambient temperature. The dark violet crystalsappeared was filtered out, and dried overP+Oro.
Synthesis of [Fe(pic)31 [LiCr(ox[] complexTo suspension of Ag[C(ox]l (0.34
gram, 0.5 mmol) in l0 mL methanol wasadded a solution of LiCl (0.063 gram, 1.5rnmol) in the same solvent (3 mL). The white
SII-!F!I II 13 Maret 20lOParalel F
precipitate AgCl was filtered out. The gre€trsolution obtained was added to solution of[Fe(pich][BF4]2 (0.30 gram, 0.5 mrnol) in 5mL water. The red precipitate was filtered
. . and dried over PcOro.
3. Result and l)iscussion3.1 Synthesis of [Fe(pic)31 [LiCr(ox)31
Polymeric ComplexThe coordination polymer
t{e(nrc):ltLiC(ox)31 was synthesised by *readdition of a solution of the iron(U) picotiniccation in water to a sotution of the tris_oxalate chrome complex with an excess ofmonovalent metal lithium. The compordwas obtained as red microcrystals in 69.6S% yield.
The general synthetic pathway for ttecomplexation reaction taking place, may berepresented as follows.
Ks[C(ox):] (aq) * 3AgNO3 (aq) -)Ag[Cr(ox[] t,t + 3 KNO3 1uq;
Ag[C(ox)3] cr,r^",ourl + 3LiCl (Metorf-+ [LiC(ox)rJ'{n.,or1 + 3AgCl cl
[Fe(pic)s]2i"qi + [LiC(ox)r]2inr",orn[Fe(pic)3] piCr(ox]l
1,1
This compound is Stable in air and is solublein some organic solvent are dimetilformamida and dimetil sulfoxida, but attemtsto obtain single crystal suitable for x-raystructure determination, has so far beenunsuccesfull. However, the polymercomplex was further characterized on thebasis of the following results. The formulaof the complex was resulted from elementalcontends has been listed in Table l.
The formula of the compound wasalso supported by infrared spectrum. Thespectmm of the complex is shown in Figurel. The absorbtion peak at 3429 cm-l wasindicated a streching vibration of OH fromligand picolinic. Streching vibration CHaromatic ring is shown at 3109 cmr-Streching vibration C:O from carboxil'ategroyp shifted to higher frequency of l7l3cm-', which indicates that it has been affectedupon coordination to metal ion. At the sarretime, v(CO) streching at 1080 cm-ris shiftedto lower frequency suggest the weakeningof v(CO) and formation of stronger bond
i.$
I
Table 1. The metal ion and c, H and N contents of polymer complex
369 Makalah PendamPing Kimia
benveen Fe-O. The strongest shift is
observed for v(C:N) bands of pyridin ring at
1597, which is a proof fo direct bonding ofpyridine nitrogen atom to the iron(Il) ' The
The presence ofband at frequency 455
ctrn-r is due to streching vibration Fe-O'
Another band appeared in spectra of the
complex at 416 cml attributed v(Cr-O), itindiiates that the oxygen atom in oxalate-
bridged Soup coordinate to metal from the
chrome atom.The powder X-ray difraction pattern
of [Fe(pic)r][LiC(ox)r] showed that the
compound has a cubic cell. The space group
of [Fe(pic]l[LiC(ox[] derived from the
Rietica program was P213, a=15.2840(18) Aaad Z=4. Typical Le Bail plot are shown in
SN'IIPK II 13 Maret 2010Paralel F
bands at frequencY 1380 and 810 cm-'
indicated oxalate as bridge liganra. Streching
vibration Fe-N was been obserued at 513 cm-''
Figure 2. The model of the structure of the
Rietveld refinement was built by reference to
that of tco(bpy)sltliC(ox)rl. In this model,
the compound consists of three-dimensional
oxalate back-bone, which provides perfect
cavities with regard to size and geometry forthe [Cotr(bpy)3]2* ions. The site symmetry ofboth the both the tris-oxalate as well as tris-
bipyridyl complexes is C3. The rather loose
oiutat" network is stabilised by the tris-
bipyridil complexes through electrostatic
interactions from n-overlap between oxalate
and bipyridine along the trigonal axis'
105.0
$T
100.0
9s.0
90.0
85. 0
80.0
75-O
3500.0 3000.o 2500-0 2qoo.o 1?50'O 1500'0 L250-0rrrn Sgrt a.DZU 8400 ZUL : FAI{Ir4AH1 { 13 -12-06 )
500. o1y'cm4000,0
- scan
[Fe(pic)3][LiCr(ox[]
* Calculated
1 '2 I zszt'g
I ',[n,.,152715
o
Figure 1. The IR spectrum of [Fe(pic)3][Lic(ox):J
370 Makalah Pendamping Kimia
IFe(pic)3][LiCr(CzOa)a]
3,m0
2,m
?ru
1,Sm
1,m0
flto
0
-ffi
ffi? thete {deg}
Figure 2. I* ryI refinement plot showing the observed (+;. Calculated (solid line) and difgr x-ft powder pattern diffraction profile of ;r"1pi"1rltlic(ox):1. rrr"-ti"tshow the positions of the allowed Bragg reflecyions in rpu"i grrup irir3.
3.2. Magnetic Pnoperties of[re(pic)d[LiCr{ox)3|
(Itc3ot>
The magnetic behaviour of compoundfFe(pic)d[LiC(ox]l under the form of I,and l/26y versus T plots is shown in Figure 3.The X value remains almost constant down to100 K while cooling down from 300 K andstarts to increase below 100 K followed by arapid increase rapidly below 40 K. In ihetemperature region 100 K < T < 300 K, 76values obey the Curie-Weiss law
C(Z= )h + , U"*).
The Tr:r, obtained
for the compound is 7.13 K with C = 4.06emu K mol'r. The positiv T6p valuesindicates the near neighbor magneticexchange interaction in the compound isferromagnetic. At.room temperature 26yT is3.89 emu K mol-r, which lower than thatexpected for magnetic interaction betweenFe(tI) and Cr(Itr) ions (4.96 emu K mol-r).
Upon coolingdecreases, reaching a3.48 emu K mol-r.
26MTminimum vahe
0.7
6o ocoE> 0.3Fo{0
0.6
05
0.1
0.0
o 40 80 1m i6o 2oo 240 2e sCD
T (K)
Figure 3. Temperature dependence of 61fr[Fe(pic)3][LiC(ox):]
37 1 Makalah PendamPing,Kimia SI*-KPK IL 13 Maret 2010Paralel F
Oxalate Dianion), . InorganicChenristry, 40, 113 * 120.
Coronado, E., Gal6n-Mascar6s, J. R',
G6mez-Garcia, C. J., and Martinez-Agudo, J. M., Martinez-Ferero, E., 2001,
Layered , Molecule-Based Magnets
Formed by DecamethylmetalloceniumCations and Two-Dimensional BimetallicComplexes {lMtrRultr(ox)3] (Mtr =Mn,Fe, Co, Cu and Zn; ox = oxalate/,
. Journal of Solid State Chemistry, 159,
391- 402.Pointillart, F;, Train, C. , Gr.ucelle, M.,
Villain, F., Decutins, S. and Verdagueq
M., 2004, Chiral Terlplating Activity ofTris(bipyridine)ruthenium(Il) Cation in
. the Design of Three-Dimensional (3D)
Optically Active Oxalate-Bridged
{ tRu(bpy)rl[Cu2"l'Ii211-.(Czon):i ]n (0 < x< 1; bpy o 2,2'-bipyridine): Structural,
Optical, and }vtragnetic Studies, Chemicul
Material,' 16, 832-841.
Coronado, E., Gali{n-Mascar6s, J:R.,' G6mez-
Garcia,:C. J', Marti-Gastaldo, C., 2005'
Synthesis,' Stnrcture, and Magaetic
Pioperties of the Oxalate-Based
Bimetallic Ferromagneti Chain {tK(18-crown-6)lMn(Hzo)zCr(ox):l)* (18-
crown-6 = Cr2H;o6, oi = Czof),Inorg*tic C.hemisW, 44, 6197'5202'
Coronado, 8.,'Gal6n-Mascar6s, J'R', :Marti-
Gastaldo, C., 2006, 'sYnthesis and
Characterization of a Soluble BimetallicOxalate-Based Bidemensional Magnet:
[K( I 8-crown-6)]: Mni(HzO)a {Cr(ox)3 } 31,
Inorganic ChemistrY,4s, 1882- I 884'
Ovanesyan , N. S., Shilov, G.V., Pyalling, A'A., Train C., Gredin, P', 2A04,
Structural and Magnetic Properties ofTwo- and Three-dimensional Molecule-
Based Magnets (catfttrntrU'o(CrOo)ul-,
Jonrnal of Magnetism and Magnetic
Materials, 212'27 6, 1 089- I 090.
Coronado E., Gal6n-Mascar6s, J'R',
Cimenez-Saiz, C-, G6mez-Garcia, C'J',
2003, Magnetic Properties of HybridMolecular Materials Based on Oxalato
Complexes, P olyhedron, 22, 2381-2386'
Pellaux, R., Schmalle, W. H., Huber, R',
Fischer, P., Hauss, T., Ouladdiaf,El., and
Decurtins, S., 1997, Molecular-BasedMagnetism in Bimetallic Two-Dimensional Oxalate-Bridged Networks'
T(K}
Figure 4. Fitting the plot of molar magnetic
suscePtibilitY vs temperatur for
tFe(pic)d[LiCr(ox):] :
ConclusioasThe polymeric complex of fonnula
[Fe(pic[]tlicr(ox)d has bsen synthesized'
FormuU of the complex has been supaorted
by metal ion contents, the elemental C,, H, Ndata, ff-m spectra in 400 - 4000 cm-'' The
crystal structure was anBlyzed by Rietveld
*Lthod with the powder X-ray diffraction
data. The space group of the compound is
Y2$. From the results of magrretic
rneasurement for [Fe(pic)r] [LiC(ox):], it was
the comPound show ferromagnetic
behaviour.
AcknowledgmentAuthors thank for financial support
from Direktorat Jendral Pendidikan
Tinggi (Dikti), Research Grant No'
SZaSPPPPP/DP2M/IU2006, as well as
Program Studi Kimia Institut Teknologi
Bariclung, University Kebangsaan Malaysia
for providing t'acilities and support to the
success ofthe studY.
ReferencesCoronado, E., Galin-Mascar6s, J' R',
G6mez-Garcia, C. J., and Martinez-
Agudo, J.M., 2001, Molecule-BasedMagnets Formed by Bimetallic Three-
Dimensional Oxalate Networks and
Chiral Tris(biPYridYl) ComPlex
Cations. The Series
lzu(bpyhl [Cl04] [Milcru'(or)r],,(Zu=Ru, Fe, Co, andNi; M":Mn,Fe, Co, Ni, Cu, and Zn; ox :
-i0 6 d0'{o oo & rooruotloteorma0zo2'40260280?00320
372 Makalah Pendamping Kimia
An X-ray aad Neutron Diffraction Study,Inorgonic Chemistry, 36, 2301 - 2308.
Tamaki H., Zhong 2.J., Matsumoto N., KidaS., Koikawa M., Achiwa N., Achiwa N.,Hashimoto Y., Okawa H,1992, Designof Metal-Complex Magnets. Synthesesand Magnetic Properties of Mixed-MetalAssemblies {NBu4[MC(ox):]],, (NBu =Tetra(n-butylammonium Ion; ox'- =Oxalate Ion; M : Mn2*, Fet*, Co'*,Ni2*, Cu2*, Zn'*), Jouruol of AmericanChemicol Society, ll4, 6974 - 6979.
Ohba M., Tamaki H., Matsumoto N., OkawaH., 1993, Oxalate-Bridge DinuclearCr(Itr)-M(II) (M=Cu, Ni, Co, Fe, Mn)Complexes: Synthesis, Structure, andMagnetism, Inorganic Chemisny, 32,5385-s390.
Decurtins, S., Schmalle, W. H., SchneuwlyP., Ensling, J., and Giitlich, P., 1994, AConcept for the Synthesis of 3-Dimensional Homo- and BimetallicOxalate-Bridged Networks [I\vlz(oxh],.Structural, Mdssbauer, and MagneticStudies in the Field of Molecular-BasedMagnets, Journal American ChemicalSociety., 116, 9521 - 9528.
Decurtins, S., Schmalle, W. H., Pellaux, R.,Schneuwly, P., and Hauser, A., 1996,Chiral, Three-DimensionalSuprarnolecular Compounds: Homo-and Bimetallic Oxalate and 1,2-Dithiooxalate-Bridged Networks. AStructural and Photophysical Study,Inorganic Chernistry, 35, 1451 - 1460.
-qParaHf
Palmer, R. A.. Piper, T.S., Inorga&Chemistry, 1966 5,864.
Glerup J., Goodson P.A., Hodgson DJ-1995, Magnetic Exchange thrc.*Oxalate Briges: Synthesis adCharacterization of (p-Oxalafdimetal(Il) Complexes of Manganesc"Iron, Cobalt, Nickel, Copper, and Zim,Inorgan ic C he mis try, 3 4, 625 5 -62@.
Min, Kil Sik., Rheingold, A. L., and Milk-J. S., 2005, Synthesis, Structure, adMagrretic Ordering of Layered (2-D) Y-Based Tris(oxalato)metalates, Inorg-Chem., 44,8433 - 8441.
Verdaguer M., Rational Synthesis dMolecular Magnetic Materials : ATribute to Olivier Khan, Polyhe&ua2001,20,1 I 15-l 128.
Wang H.D., Li Y.T.. Yan C.W., Zeng X-C-Synthesis and Magnetic Properties of pOxalate-Bridged Cu(lI)-Fe(IID-Cu(tr)Heterotrinuclear Complexes, PolichJournal C hemistry, 2002, 7 6, 637 -644.
Zhang L., Bu W.M., Yan S.P., Jiang Z.H-LiaoD.Z, Wang G.L., Weaker MagneticInteractions of Oxalato-Coppe(Il)Binuclear Compounds: Synthesb,Spectroscopy, Crystal Stnrcture andMagnetism, Polyhedron, 2000, 19, 110!1110.