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：2009-11-25。：2009-12-25。(No.20601015，20871072)、(No.2007BS04023)(No.2009ZRA02071)。＊。E-mail：qdplastics@163.com：，，38，；：。Zn髤、＊,12222(1，100083)(2，266042)：2{[Zn(ip)(Eim)2]·H2O}(1)Zn(ip)(Mim)2(2)(ip，Eim1-，Mim1-)，X。2azigzag,Zn22N，。2，1O-H…O。12Zn2+/Zn+。：；髤；；：O614.24+1：A：1001-4861(2010)04-0609-06TwoZn髤CoordinationPolymersBasedonIsophthalateandImidazoleDerivatives:Synthesis,CrystalStructures,andElectrochemicalPropertiesLIRong-Xun1DENGYue-Yi2LIUBao-Cheng2LIUFa-Qian＊,2WUQi-Ye2(1SchoolofMaterialsScienceandEngineering,UniversityofScienceandTechnologyBeijing,Beijing100083)(2KeyLaboratoryofAdvancedMaterials,QingdaoUniversityofScienceandTechnology,Qingdao,Shandong266042)Abstract:TwoZn髤coordinationpolymers{[Zn(ip)(Eim)2]·H2O}(1)andZn(ip)(Mim)2(2)(whereip2-=isophthalatedianion;Eim=1-ethyl-1H-imidazole;Mim=1-methyl-1H-imidazole),havebeensynthesizedandcharacterizedbyX-raysinglecrystaldiffractometry.Complexes1and2containpolymericzigzagchainsextendedalongaaxis,andeachZn髤atomistetrahedrallycoordinatedtotwoOatomsfromdifferentisophthalateionsandtwoNatomsfromEimorMim.ThereareonlyvanderWaalsinteractionsbetweenthechainsin2,while1DZigzagchainsin1areconnectedtoforma3DnetworkbyO-H…Ocontacts.TheelectrochemicalstudiesrevealthatredoxesofZn2+/Zn+inthecomplexes1and2arequasi-reversibleprocesses.CCDC:762257,1;762258,2.Keywords:isophthalatecompound;Zn髤carboxylate;crystalstructure;cyclicvoltammetryThecrystalengineeringapproachisextensivelyusedtocontrolmaterialstructureanddimensionality[1-3].Thecrystalengineeringofcoordinationpolymershasheldgreatpotentialforapplicationsinmanyareas,suchasmolecularmagnetism,heterogeneouscatalysis,molecularsieving,storage,andnon-linearoptics[4-9].Bridgingmetalswithorganicligandsisusedtoconstructlowerdimensionalcoordinationpolymers,whichcanbefurtherassembledbyhydrogen-bonding,π-πinteractionorotherintermolecularcontactstoform26420104Vol．26No．4609-614CHINESEJOURNALOFINORGANICCHEMISTRY26extendednetworkswithhigherdimensionality[10-12].Ontheotherhand,moresubtleconditionscanalsobeusedtomodifystructures,suchaschoiceofsolventsorcounterions.Byjudiciouschoiceofbridgingligandsandmetalcoordinationgeometries,controloverthetopologyandgeometryoftheinfinitenetworkscanbegained.LotsofZn髤coordinationpolymersbasedonisop-hthalateasbridgingligandsandN-donorsasauxiliaryligandshavebeenreported[13-20],butonescontainingN-donorsofimidazolederivativesarerare[21-23].Imidazolederivativescannotonlycoordinatewithmetalion,butalsodonatehydrogenbonds,whichmayresultintheformationofhigherdimensionalstructures.Herewereportoncrystalstructuresandcharac-terizationoftwocoordinationpolymers,{[Zn(ip)(Eim)2]·H2O}(1)andZn(ip)(Mim)2(2).The1DZigzagchainsin1and2areassembledtoform3DnetworksbyhydrogenbondsandvanderWaalsinteractions,respectively.1Experimental1.1MaterialsandinstrumentsAllthechemicalreagentsforsynthesizingthetitlecompoundswerepurchasedcommerciallyandusedwithoutfurtherpurification.Elementalanalyses(C,HandN)werecarriedoutonaPerkin-Elmer1400Canalyzer.VoltammetrywasperformedbyusingaCHI832Belectrochemicalanalysissystem(China)withathree-electrodesystemconsistingofaglasscarbon(GC)electrode(U=3mm)astheworkingelectrode,asatur-atedcalomelelectrode(SCE)asthereferenceelectrode,andaplatinumwireastheauxiliaryelectrode.Alltheelectrochemicalmeasurementswerecarriedoutina10mLelectrolytecellwith0.01mol·L-1pH6.86KH2PO4-Na2HPO4buffersolutionaselectrolyte.TGcurvewasrecordedonaNETZSCH-TG209GmbHthermoanalyserinflowofN2,inthetemperaturerangefrom20~700℃,withaheatingrateof10℃·min-1.1.2PreparationComplex1waspreparedasfollows.ZnSO4·7H2O(1.15g,4mmol)wasaddedtoasolutionofEim(0.75g,8mmol)in10mLofdistilledwaterand40mLofethanol.Theresultingsolutionwasaddedtoasolutionofdisodiumisophthalate(0.84g,4mmol)in10mLofdistilledwaterand40mLofethanol(undercontinuousstirringatroomtemperature),andthemixturewasrefluxedfor7h.Thepowderprecipitateformedwasfilteredoff,andthecolorlessfiltratewasallowedtostayatambienttemperatureforaperiodofabout3weeks,gave0.53g(24%yields)ofcolorlessblockcrystalssuitableforstructuraldeterminations.Anal.Calcd.forC18H17ZnN4O5:C49.27,H4.82,N12.77;found:C50.01,H4.99,N12.82.Thecolorlesscrystalofcomplex2wasobtainedbyasimilarprocedureasfor1exceptforusingMim(0.66g,8mmol)insteadofEim,yield:0.45g,49%.Anal.Calcd.forC16H16ZnN4O4:C48.81,H4.10,N14.23;found:C48.72,H4.02,N14.49.1.3CrystalstructuredeterminationSinglecrystalsof1and2weremountedonaBrukerSMART1000CCDareadetectorX-raysinglecrystaldiffractometerwithgraphite-monochromatedMoKαradiation(λ=0.071073nm)andaφ/ωscanningmodeat293(2)K.IntensitieswerecorrectedforLorentzandpolarizationeffectsandempiricalabsorption.ThestructurewassolvedbydirectmethodsviaSHELXS97program[24]andrefinedbyfull-matrixleastsquaresonF2viaSHELXL97program[25].Allthenon-hydrogenatomswerelocatedfromthedifferenceFouriermapandrefinedanisotropically.Hatomswerepositionedgeometrically(C-H=0.093nm,0.096nm)andallowedtorideontheirparentatomswithUiso(H)=1.2timesUeq(C).Crystallographicdatafor1and2arelistedinTable1.CCDC:762257,1;762258,2.Table1Crystallographicdataforthecomplexes1and2Com