吡嗪-2,3,5,6-四羧酸配位聚合物的合成 结构及性质研究-study on the synthesis structure and properties of pyrazine - 2,3,5,6 - tetracarboxylic acid coordination polymer.docx

摘要配位聚合物由于其结构的多样性及独特的物理性能而成为近年来人们关注的焦点。在磁性材料、催化、电化学、分子识别、离子交换、气体储存等领域具有潜在的应用前景。吡嗪羧酸类配体因其配位能力强以及配位模式的多样性，因而备受人们的广泛关注。吡嗪-2,3,5,6-四羧酸是一类含有N、O多齿功能的氮杂环配体，能与不同的金属以不同的配位方式进行配位,有利于形成结构新颖的配合物。本论文选用吡嗪-2,3,5,6-四羧酸作为配体,通过室温溶剂挥发，合成出了两种新的配位聚合物：[Cu2(PZTC)(NH3)2(H2O)2]·2H2O(2)，稀土异核配合物[Eu0.5Tb0.5(H2PZTC)(H2O)6(NO3)]·HNO3·H2O(5)，并利用X-ray单晶衍射，红外光谱(IR)，荧光分析及元素分析，电感耦合等离子光谱发生仪(ICP)等手段对它们进行结构表征和分析。配合物的荧光研究结果表明，稀土异核配位聚合物(5)的荧光是由金属离子到配体的电荷转移(MLCT)所致，并且荧光强度较单一配合物有较明显的增强。同时采用溶剂挥发法在酸性条件下探索了3d-4f异核金属配位聚合物合成的可能性。通过ICP检测，仅得到了单一的稀土配合物，表明在酸性条件下，稀土离子更容易与吡嗪-2,3,5,6-四羧酸相配位。关键词：吡嗪-2,3,5,6-四羧酸；配位聚合物；荧光分析；结构分析；稀土配合物IAbstractInrecentyears,considerableinterestshavebeenfocusedonthecoordinationpolymersbecauseoftheirnovelstructuresanduniquephysicalproperties.Inaddition,thesecomplexesexhibitpromisingapplicationsinmagneticmaterials,catalysis,electrochemistry,molecularrecognition,ion-exchangeandgasstorageaswell.Pyrazinecarboxylateligandshaveattractedintenseinterestduetotheirstrongcoordinationcapabilityandvarietiesofcoordinationmodes.Pyrazine-2,3,5,6-tetracarboxylicacidisamultifunctionalN-heterocyclicligandwithN/O-donorsandcouldbeemployedinlinkingdifferentmetalatomswithdifferentcoordinativemodes,resultinginunexpectedcomplexeswithnovelstructures.Inthisdissertation,pyrazine-2,3,5,6-tetracarboxylicacid(H4PZTC)isselectedasthebuildingblock,twocoordinationpolymershavebeensynthesizedundersolventevaporationmethodatroomtemperature.Theywere[Cu2(PZTC)(NH3)2(H2O)2]·2H2O(2),[Eu0.5Tb0.5(H2PZTC)(H2O)6(NO3)]·HNO3·H2O(5).TheywerewellcharacterizedbysinglecrystalX-raydiffraction,infrared(IR)spectroscopy,luminescentanalysis,elementalanalysis,andInductivelyCoupledPlasma-AtomicEmissionSpectrometer(ICP)，respectively.Luminescentstudiesonhetero-metalcoordinationpolymer(5)showedthattheemissionofcomplex(5)isassignedtotheemissionofmetal-to-ligandchargetransfer(MLCT).Inaddition,complex(5)hadrelativeobviousluminescentenhancementeffectcomparingtosinglecomplexes.Inaddition,weexplorethepossibilityof3d-4fhetero-metalcoordinationpolymers,whichwassy