兩個(gè)基于間苯二甲酸和咪唑衍生物Zn髤配位聚合物的合成_晶體結(jié)構(gòu)和電化學(xué)性能_英文

1、第26卷第4期2010年4月無(wú)機(jī)化學(xué)學(xué)報(bào)CHINESEJOURNALOFINORGANICCHEMISTRYVol26No4609-614兩個(gè)基于間苯二甲酸和咪唑衍生物Zn髤配位聚合物的合成、晶體結(jié)構(gòu)和電化學(xué)性能李榮勛,1鄧月義2劉保成2劉法謙2吳其曄2100083)(2青島科技大學(xué)新材料研究重點(diǎn)實(shí)驗(yàn)室，青島266042)摘要：合成了2個(gè)配位聚合物Zn(ip)(Eim)2·H2O(1)和Zn(ip)(Mim)2(2)(ip為間苯苯二甲酸陰離子，Eim為1-乙基咪唑，Mim為1-甲基咪唑)，并用X射線單晶衍射儀測(cè)定了其晶體結(jié)構(gòu)。2個(gè)配合物的結(jié)構(gòu)中都含有沿晶體a軸方向的zigzag聚合鏈

2、,每個(gè)Zn原子分別與2個(gè)來(lái)自不同間苯二甲酸離子氧原子和2個(gè)來(lái)自乙基咪唑或甲基咪唑的N原子配位，形成了配位四面體。在配合聚合物2中各鏈間只存在范德法力相互作用，而在配合物1中一維鏈通過(guò)O-HO氫鍵相互作用進(jìn)一步連接形成了三維網(wǎng)絡(luò)結(jié)構(gòu)。電化學(xué)研究表明在配合物1和2中Zn2+/Zn+對(duì)的氧化還原是一個(gè)準(zhǔn)可逆的過(guò)程。關(guān)鍵詞：間苯二甲酸配合物；羧酸鋅髤鹽；晶體結(jié)構(gòu)；循環(huán)伏安法中圖分類號(hào)：O614.24+1文獻(xiàn)標(biāo)識(shí)碼：A文章編號(hào)：1001-4861(2010)04-0609-06(1北京科技大學(xué)材料科學(xué)與工程學(xué)院，北京TwoZn髤CoordinationPolymersBasedonIsophthalat

3、eandImidazoleDerivatives:Synthesis,CrystalStructures,andElectrochemicalPropertiesLIRong-Xun1DENGYue-Yi2LIUBao-Cheng2LIUFa-Qian,2WUQi-Ye2(1SchoolofMaterialsScienceandEngineering,UniversityofScienceandTechnologyBeijing,Beijing100083)(2KeyLaboratoryofAdvancedMaterials,QingdaoUniversityofScienceandTechn

4、ology,Qingdao,Shandong266042)Abstract:TwoZn髤coordinationpolymersZn(ip)(Eim)2·H2O(1)andZn(ip)(Mim)2(2)(whereip2-=isophthalatedianion;Eim=1-ethyl-1H-imidazole;Mim=1-methyl-1H-imidazole),havebeensynthesizedandcharacterizedbyX-raysinglecrystaldiffractometry.Complexes1and2containpolymericzigzagchain

5、sextendedalongaaxis,andeachZn髤atomistetrahedrallycoordinatedtotwoOatomsfromdifferentisophthalateionsandtwoNatomsfromEimorMim.ThereareonlyvanderWaalsinteractionsbetweenthechainsin2,while1DZigzagchainsin1areconnectedtoforma3DnetworkbyO-HOcontacts.TheelectrochemicalstudiesrevealthatredoxesofZn2+/Zn+int

6、hecomplexes1and2arequasi-reversibleprocesses.CCDC:762257,1;762258,2.Keywords:isophthalatecompound;Zn髤carboxylate;crystalstructure;cyclicvoltammetryThecrystalengineeringapproachisextensivelyusedtocontrolmaterialstructureanddimensionality1-3.Thecrystalengineeringofcoordinationpolymershasheldgreatpoten

7、tialforapplicationsinmanyareas,suchasmolecularmagnetism,heterogeneouscatalysis,收稿日期：2009-11-25。收修改稿日期：2009-12-25。molecularsieving,storage,andnon-linearoptics4-9.Bridgingmetalswithorganicligandsisusedtoconstructlowerdimensionalcoordinationpolymers,whichcanbefurtherassembledbyhydrogen-bonding,-interac

8、tionorotherintermolecularcontactstoform國(guó)家自然科學(xué)基金(No.20601015，20871072)、山東省博士基金(No.2007BS04023)和山東省自然科學(xué)基金(No.2009ZRA02071)資助項(xiàng)目。通訊聯(lián)系人。E-mail：qdplastics第一作者：李榮勛，男，38歲，副教授；研究方向：材料學(xué)。610無(wú)機(jī)化學(xué)學(xué)報(bào)第26卷extendednetworkswithhigherdimensionality10-12.Ontheotherhand,moresubtleconditionscanalsobeusedtomodifystructure

9、s,suchaschoiceofsolventsorcounterions.Byjudiciouschoiceofbridgingligandsandmetalcoordinationgeometries,controloverthetopologyandgeometryoftheinfinitenetworkscanbegained.LotsofZn髤coordinationpolymersbasedonisop-hthalateasbridgingligandsandN-donorsasauxiliaryligandshavebeenreported13-20,butonescontain

10、ingN-donorsofimidazolederivativesarerare21-23.Imidazolederivativescannotonlycoordinatewithmetalion,butalsodonatehydrogenbonds,whichmayresultintheformationofhigherdimensionalstructures.Herewereportoncrystalstructuresandcharac-terizationoftwocoordinationpolymers,Zn(ip)(Eim)2·H2O(1)andZn(ip)(Mim)2

11、(2).The1DZigzagchainsin1and2areassembledtoform3DnetworksbyhydrogenbondsandvanderWaalsinteractions,respectively.11.1ExperimentalMaterialsandinstrumentsAllthechemicalreagentsforsynthesizingthetitlecompoundswerepurchasedcommerciallyandusedwithoutfurtherpurification.Elementalanalyses(C,HandN)werecarried

12、outonaPerkin-Elmer1400Canalyzer.VoltammetrywasperformedbyusingaCHI832Belectrochemicalanalysissystem(China)withathree-electrodesystemconsistingofaglasscarbon(GC)electrode(U=3mm)astheworkingelectrode,asatur-atedcalomelelectrode(SCE)asthereferenceelectrode,andaplatinumwireastheauxiliaryelectrode.Allthe

13、electrochemicalmeasurementswerecarriedoutina10mLelectrolytecellwith0.01mol·L-1pH6.86KH2PO4-Na2HPO4buffersolutionaselectrolyte.TGcurvewasrecordedonaNETZSCH-TG209GmbHthermoanalyserinflowofN2,inthetemperaturerangefrom20700,·min-1.withaheatingrateof10Table1ComplexEmpiricalformulaFormulaweightC

14、rystalsize/mm1C18H21ZnN4O5438.76PreparationComplex1waspreparedasfollows.ZnSO4·7H2O(1.15g,4mmol)wasaddedtoasolutionofEim(0.75g,8mmol)in10mLofdistilledwaterand40mLofethanol.Theresultingsolutionwasaddedtoasolutionofdisodiumisophthalate(0.84g,4mmol)in10mLofdistilledwaterand40mLofethanol(undercontin

15、uousstirringatroomtemperature),andthemixturewasrefluxedfor7h.Thepowderprecipitateformedwasfilteredoff,andthecolorlessfiltratewasallowedtostayatambienttemperatureforaperiodofabout3weeks,gave0.53g(24%yields)ofcolorlessblockcrystalssuitableforstructuraldeterminations.Anal.Calcd.forC18H17ZnN4O5:C49.27,H

16、4.82,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,NCrystalstructuredeterminationSinglecrystalsof1and2weremountedo

17、naBrukerSMART1000CCDareadetectorX-raysinglecrystaldiffractometerwithgraphite-monochromatedMoKradiation(=0.071073nm)anda/scanningmodeat293(2)K.IntensitieswerecorrectedforLorentzandpolarizationeffectsandempiricalabsorption.ThestructurewassolvedbydirectmethodsviaSHELXS97program24andrefinedbyfull-matrix

18、leastsquaresonF2viaSHELXL97program25.Allthenon-hydrogenatomswerelocatedfromthedifferenceFouriermapandrefinedanisotropically.Hatomswerepositionedgeometrically(C-H=0.093nm,0.096nm)andallowedtorideontheirparentatomswithUiso(H)=1.2timesUeq(C).Crystallographicdatafor1and2arelistedinTable1.CCDC:762257,1;7

19、62258,2.1.2Crystallographicdataforthecomplexes1and2C16H16ZnN4O4393.70.20×0.10×0.100.30×0.20×0.20第4期李榮勛等：兩個(gè)基于間苯二甲酸和咪唑衍生物Zn髤配位聚合物的合成、晶體結(jié)構(gòu)和電化學(xué)性能611ContinuedTable1Temperature/KCrystalsystemSpacegroupa/nmb/nmc/nmV/nm3Z·Dc/(Mgm-3)293(2)OrthorhombicPnma1.5876(3)1.3450(3)0.97460(19)

20、2.0811(7)41.41.2159082.45250120.02250.07370.16720.12290.1919293(2)OrthorhombicPbca0.96820(19)1.3224(3)2.6983(5)3.4548(12)81.5141.4516161.51250540.01160.06800.18380.10280.2071/mm-1F(000)range/(°)ReflectionscollectedUniquereflectionsGoodness-of-fitonF2RintR1I>2(I)wR2I

21、>2(I)R1(alldata)wR2(alldata)2Resultanddiscussion2.1CrystalstructuresTheX-raydiffractionanalysisindicatesthateachZnatomadoptsadistortedtetrahedralgeometryformedbytwoNatomsfromEimorMimmoleculesandtwoOatomsofdifferentipligands(Fig.1).Thecomplexes1and2containinfinite1Dpolymericzigzagchainsconsistingo

22、fZn(L)2(L=Eimfor1;Mimfor2)buildingunitsconnectedbybridgingisophthalateligandsinthe2-1,3coordinationmode.Fig.2aandFig.2bshowafragmentofthechainsinthecomplexes1and2respectively.TheZn-OandZn-NbondlengthsarecomparabletothoseofthestructurallyanalogouscomplexZn(ip)(im)2n·3nH2O(Zn-O=0.1980(2)and0.1933

23、(3)nm,Zn-N=0.2000(3)and0.2011(3)nm)21.612無(wú)機(jī)化學(xué)學(xué)報(bào)第26卷ThebondanglesforZnatomsinthecomplexes1and2lieintherangeof95.5(3)°114.9(3)°and96.6(18)°117.2(19)°,respectively.(Table2)Inthebridgingisop-hthalateanionswithamphimonodentatecoordinationmode，theaverageC-Odistanceforthecoordinatedoxyg

24、enatom(0.1285(10)nmin1and0.1287(6)nmin2)isslightlylongerthanforuncoordinatedones(0.1221(10)nmin1and0.1208(6)nmin2).Thecarb-oxylategroupsandbenzeneringsin1arealmostcoplanar,butthedihedralanglebetweentwocarboxy-latesin2is35.33(3)°.Inthecomplexes1and2,thepolymerbackbonepropagatesalongthecrystallog

25、raphica-axis.Themetal-metaldistancesacrosseachpolymerbackboneare0.9594(21)nmin1and0.9682(21)nmin2,whichareshorterthanthosefoundinZn(ip)(im)2n·3nH2O(1.0391(14)nm)21.Theclosestmetal-metaldistancesbetweenneighboringstrandsfor1are0.9055(21)nm,whicharelongerthanthoseof0.6734(17)nmand·3nH2O21,re

26、spe-0.7438(14)nmin2andZn(ip)(im)2nctively.Inthecomplex1,theadjacentmetal-organicchainsareconnectedintoa3Dnetworkviahydrogenbondsbetweensolventwatermoleculesandtheuncoordinatedoxygenatomsofthecarboxylategroups(Ow-HWAO(4)=0.2910(14)nm),whichcontroltheTable2Selectedbondlengths(nm)andbondangles(°)f

27、orthecomplexesComplex1Zn-O(2)O(2)-Zn-O(3)O(2)-Zn-N(2)Zn-O(1)Zn-O(4)O(1)-Zn-O(4)O(1)-Zn-N(2)0.1944(6)95.5(3)111.64(17)Zn-O(3)O(3)-Zn-N(2)Complex20.1943(6)111.77(18)Zn-N(2)N(2)#1-Zn-N(2)0.2001(6)114.9(3)0.1930(4)0.1976(4)117.2(19)115.5(2)Zn-N(2)0.1996(6)Zn-N(4)0.2032(5)O(4)-Zn-N(2)O(1)-Zn-N(4)105.8(19

28、)111.5(19)O(4)-Zn-N(4)N(2)-Zn-N(4)96.6(18)108.3(2)Symmetryoperations:#1:x,-y+1/2,z.第4期李榮勛等：兩個(gè)基于間苯二甲酸和咪唑衍生物Zn髤配位聚合物的合成、晶體結(jié)構(gòu)和電化學(xué)性能613packingoftheadjacentchains(Fig.3aandTable3).Incomplex2thereareonlyvanderWaalsinteractionsbetweentheadjacentchainsincontrastto1(Fig.3b).Somepotentiallyweak(C-HO)intramole

29、cularinter-actionsexistinthecomplexes1and2(Table3),whichfurtherstabilizethestructuresofzigzagchains.Table3D-HAComplex1Ow-HWAO(4)#1C(6)-H(6A)O(4)C(13)-H(13A)O(2)Complex2C(1)-H(1A)O(3)#2C(4)-H(4B)O(3)#3C(11)-H(11A)O(2)#4Hydrogenbondsofthecomplexes1and2(nmand°)d(D-H)0.0850.0930.0930.0960.0930.093d

30、(HA)0.2500.2590.2400.2550.2310.254d(DA)0.2910(14)0.3314(8)0.2718(10)0.3421(9)0.3150(2)0.3456(6)(DHA)111135100150150171Symmetrycode:#1:1-x,-1/2+y,-z;#2:3/2-x,1/2+y,z;#3:3/2-x,1/2+y,z;#4:3/2-x,-1/2+y,z.2.2ThermalpropertiesThermalanalysesofthecomplex1revealthatthefirstweightlossofabout4.95%occursinthet

31、emperaturerangeof82250,whichcorrespondstothelossofwatermolecules(calculated4.14%).Onfurtherheatingpolymericchainsdecomposeviatwounidentifiedstepsinthetemperaturerangeof250580andtheweightlossof79.04%wasascribedtothereleaseofEimandipligands.(calculated78.21%).ThefinalproductwasZnOwiththeremainingperce

32、ntageof614無(wú)機(jī)化學(xué)學(xué)報(bào)第26卷16.68%(calculated17.65%).Forthecomplex2thefirstweightlossof40.38%around220390correspondstothelossoftwoMimmolecules(calculated41.71%).Inthetemperaturerangeof390520weightlossof38.17%wasascribedtothereleaseofipligand(calculated37.59%),togivetheexpectedoxides(observed18.95%,calculate

33、d20.61%).2.3ElectrochemistryTypicalcyclicvoltammetrycurvesforthecomplexes1and2in0.01mol·L-1pH6.86KH2PO4-Na2HPO4buffersolutionsareshowninFig.4.4BattenSR.Curr.Opin.SolidStateMater.Sci.,2001,5:107-1145HuangXC,LinYY,ZhangJP,etal.Angew.Chem.Int.Ed.,2006,45:1557-15606JaniakC.J.Chem.Soc.,DaltonTrans.,

34、2003:2781-27877RowsellJLC,YaghiOM.MicroporousMesoporousMater.,2004,73:3-128KitagawaS,KitauraR,NoroSI.Angew.Chem.,Int.Ed.,2004,43:2334-23399YamaguchiT,TashiroS,TominagaM,etal.Adv.Inorg.Biochem.,2007,15(2):468-47210LewinskiJ,ZacharaJ,JustyniakI,etal.Coord.Chem.Rev.,2005,249:1185-120511ChenHJ,ZhangJ,Fe

35、ngWL,etal.Inorg.Chem.Commun.,2006,9:300-30212SongJF,ChenY,LiZG,etal.J.Mol.Struct.,2005,743:243-24813LIBin(李彬),SUNYue-Fei(孫躍飛),GOUShao-Hua(茍少華),etal.ChineseJ.Inorg.Chem.(WujiHuaxueXuebao),2001,17(6):917-92014ZhouYF,ZhaoYJ,SunDF,etal.Polyhedron.,2003,22:1231-1235Fig.4·Cyclicvoltammetryof3.00×10-4molL-1·complexes1and2in0.01molL-1pH6.8615WangSP,GaoDZ,LiaoDZ,etal.TransitionMet.Chem.,2006,31:214-22816HaoZM,ZhangXM.Inorg.Chem.Commun.,2006,9:57-6217CheGB,LiuCB,LiuB,et