基于多羧酸超分子配合物的构筑与结构研究-study on the construction and structure of supramolecular complexes based on polycarboxylic acids.docxVIP

AbstractInrecentyears,supramolecularcomplexesconstructedbycarboxylicacidsthroughbothcovalentbondandweakinteractionshaveattractedgreatinterestofchemists.Thisisnotonlybecauseoftheirintriguingstructuralframeworksbutalsoaccountfortheirpotentialapplicationsincatalysis,electronicandmagneticmaterials,microporousmaterialsandnonlinearopticsmaterials.Inthisthesis,aseriesofcomplexesbasedonaromaticmulticarboxylicacidshavebeensuccessfullysynthesizedinsolutionsorunderhydrothermalconditions.Theirstructureandpropertiesareinvestigated.Fourdiscretestructuralcomplexesweresynthesizedinthesolutionwiththeligandp-phenylenediamine--N,N,N?,N?-tetraaceticacid(p-PhDTA)and2,2’-bipyridine,pyridineandoxalate:[Ni2L(2,2′-bipy)2(H2O)2]·4H2O(1)，[Co2L(2,2′-bipy)2(H2O)2]·4H2O(2)，[Co2L(pyridine)2(H2O)4]·4H2O(3)，[Gd2(C2O4)(H2L))2(H2O)10]·6H2O(4).TheIRspectraandX-raydiffractionsrevealthatcomplexes1-3aredinuclearwhichwasbridgedbythep-PhDTAligandintheircrystals.Theligandp-PhDTAishexdentateandthecentralionsareallsixcoordinatedinadistortedoctahedralgeometry.Therearealotofcrystalwatersandcoordinatewatersinthecomplex.AbundanthydrogenbondsareobservedbetweenthesewatersanduncoordinateOfromcarboxylicgroup.Hydrogenbondsextendthediscretestructureinto2Dor3Dsupramolecularstructure.Thereareπ-πstackinginthecomplexbetweenthearomaticringsandheteroatomicrings.Thestackingeffectmakesthesupramolecularstructuremorestable.Complex4containstwomonodentatep-PhDTAinitsstructure.Thetworareearthionsarebridgedbytheoxalateligandandtherearefivecoordinatewatersineachunit.Sixcrystalwatersarearoundthemainstructure.Thecoordinatewatersanduncoordinatedwatersareservedbothasdonorandacceptertogivea3Dhydrogennetworkinthecrystalofcomplex4.Threeonedimensionalchaincoordinatepolymerbasedon2,5-pyridinedicarboxylicacidaresynthesizedinsolution:{[Co(H2O)4][Co(C7H3O4N)2(H2O)2]·4H2O}∞(5),{[Mn(H2O)4][Mn(C7H3O4N)2(H2O)2]·4H2O}∞(6),{[Cu(C7H3NO4)(H2O)]·2H2O}∞(7).TheX-raydiffractionsshowthatcompound5and6areisomorphous.Thecarboxylicgroupintheortho-positionofNinth