刚性芳香羧酸类配合物的合成 结构解析及性质分析-structural analysis and property analysis of rigid aromatic carboxylic acid complexes.docxVIP

AbstractTherationaldesignandsynthesisofcoordinationcompoundsareofgreatinterest,owingtotheirelegantframeworktopologiesaswellastheirtremendouspotentialapplicationsinnonlinearoptics,catalysis,luminescence,gassorption,andmagnetism.Studiesinthisfieldhavebeenfocusedonthedesignandconstructionofnewcoordinationframeworksaswellastheelucidationoftheirstructure-functionrelationship.Twelvecoordinationcompoundsformulatedas[Tb(ctd)(DMF)]n(1)，[Dy(ctd)(DMF)]n(2),[Mn2(pip)2(H2O)4]·4H2O(3),[Cd(pip)(H2O)2]·H2O(4),[Mn(pip)(H2O)2]·H2O(5),[Mn(pip)(4,4′-bipy)](6),[Co(pip)(4,4′-bipy)](7),[Co(pip)(pyz)](8),[Zn(Hpip)(HCO2)]·2H2O(9),[Mn3(pip)2(HCO2)2(H2O)2](10),[Co3(pip)2(HCO2)2(H2O)2](11)and[Zn(pip)(H2O)]·2H2O(12),werepreparedbysolvothermalreactionsbasedon[5′-carboxyl-[1,1′:3′,1′′-terphenyl]-4,4′′-dicarboxylicacid(H3ctd)and5-(Pyridin-4-yl)isophthalicAcid(H2pip).Allcompounds1-12werecharacterizedbyelementalanalysis,IRspectraandX-raysingle-crystaldiffraction.EightofthemweremeasuredbythermalgravimetricanalysisandpowderX-raydiffractionanalysis.Structuralanalysesrevealthatthecompound1and2areisostructural,andeachformsathree-dimensional(3D)structurepossessingone-dimensional(1D)channelsfilledwithcoordinatedDMFmolecules.Compounds3,4and5possesstwo-dimensional(6,3)layeredstructuresandfurtherassembledintoa3Dframeworkviaπ-πstackingandH-bondinginteractions.Inaddition,4and5arealsoisostructural.Compounds6-9displaytwo-foldinterpenetrating3Dpillar-layernetwork.Theadjacentlayersareconnectedthrough4,4′-bipy,pyrazine(pyz)andformateaslinkers.Theresultantthree-dimensionalarchitectureof6-8canbesimplifiedasa(3,5)-connectedhmsnetwork,andcompound9exhibitsa(3,4)-connected3DfscframeworkwiththeSchl?flisymbolof{63}{65.8}.Compounds6and7arealmostidenticalinstructure.Compounds10and11areisomorphousandpossessnovel3Dframework,theyaretrinuclearcomplexes.Therearedinuclearzincringsincompound12,anditexhibitsa(3,6)-connected2Dbilayerkgdnetworkwith{43}2{46.66.83}topology.Moreover,thephotoluminescencepropertiesof1and2havebeeninvestigate