双咪唑类配位聚合物的构筑及其荧光性质分析-construction of diimidazole coordination polymers and analysis of their fluorescent properties.docx

ConstructionandPhotoluminescentPropertiesofCoordinationPolymersBasedonBis-imidazoleDerivativesAbstractCoordinationpolymershaveattractedmuchinterestduetotheirintriguingarchitecturesandpotentialapplicationsinabsorption,separation,magnetism,luminescenceandcatalysis,etc.Recently,theemploymentoftheself-assemblyofmetalsaltswithdi-ormulti-carbolylicacidsand/ormultidentateN-donorheterocyclicligandshasbecomeaneffectiveapproachforconstructingcoordinationpolymers.AmongnumerousN-donorligands,bis-imidazolylligandswithstructuraldiversitieshavebeenwidelyused.Studiesoftherelationshipbetweensubstitutedgroupsorspacergroupsoftheseligandsandthearchitectureofthegeneratednetworksarelessreported.Inthisthesis,weperformUllmanncouplingsofaryldi-bromidesandimidazolederivativesatsolidphaseusingmicrowaveheatingtoaffordninebis-imidazolederivatives.Wechosebis-imidazolylligandspossessingdifferentsubstitutedgroups(NH2orNO2)orspacergroups(bibenzeneor9H-carbazole)toreactwithpolycarboxylatesandmetalions.Finally,aseriesofcoordinationpolymerswereobtained.Weinvestigatedtheircrystalstructuresandphotoluminescentproperties.Theseresultswerebrieflydescribedasfollows:ThereactionsbetweenCd(II)salt,bimband5-R-1,3-H2bdcderivatives(R=H,Me,NH2,OH,NO2,SO3H)gaverisetosixcoordinationpolymers:[Cd(5-R-1,3-bdc)(bimb)]n(R=H(1),R=Me(2),R=NH2(3),R=OH(4));{[Cd2(H2O)(5-NO2-1,3-bdc)2(bimb)]·2H2O}n(5);[Cd(5-SO3-1,3-Hbdc)(bimb)]n(6).Duetodifferenteffectofthesubstituentgroupsof5-R-1,3-bdc,1–4exhibitsimilarpillared-layerframeworksinwhich2D[Cd4(5-R-1,3-BDC)4]n(R=H,Me,NH2andOH)layersareinterlinkedbybimbligands.5hasatwo-foldinterpenetrating3Dframeworkinwhich1D[Cd2(5-NO2-1,3-BDC)2]nchainsareinterconnectedbybimbligands.6showsa3D(3,5)-connectedframeworkinwhich2D[Cd2(5-SO3-1,3-HBDC)2]nnetworksarebridgedbybimbligands.英文摘要双咪唑类配位聚合物的构筑及其荧光性质研究Thereactionsofmetalsalts(Mn(II),Co(II),Ni(II)andCd(II)),bimbwithH2bpdb,H3OAIPandH2tpdcgaverisetoninecoordinationpolymers:[Ni2(HOAIP)2(bimb)3(H2O)2]n(7);{[Cd3(OAIP)2(bimb)(H2O)2]·2H2O}n(8);[M(H2O)2(bpdb