芳香二羧酸类功能晶态材料的合成 结构与性能分析-synthesis structure and performance analysis of aromatic dicarboxylic acid functional crystalline materials.docxVIP

内容摘要本论文从材料的应用与功能性出发,基于联苯类芳香二羧酸有机组件，通过引入不同的含氮辅助组件,设计合成了18种金属有机晶态材料,主要研究了它们合成条件、影响因素、拓扑结构以及光磁性能。按所用有机组件的不同，本文研究内容分为三部分：一,配体构型对结构维度的影响。基于3,3-联苯二甲酸,通过引入具有不同配体构型的含氮辅助组件获得了晶态材料1~6，包括与螯合含氮组件组装的具有一维链状结构的晶态材料1~3以及与桥联含氮组件组装的具有三维拓扑结构的晶态材料4~6;二,配体长度对结构维度的影响。基于2,4-联苯二甲酸，通过调控桥联含氮组件的长度，获得两组结构维度因辅助配体长度改变而增加的晶态材料7~10和11~14;三,配体空间位阻对结构的影响。基于9-芴酮-2,7-二羧酸，获得因螯合含氮配体空间位阻增加导致由金属中心与羧酸配体构筑的次级链状结构单元更加离散的晶态材料15~17，以及与桥联含氮配体合成的具有三维结构的晶态材料18。本论文对以上晶态材料的结构及性能都做了相关表征和详细分析，并着重探索了辅助含氮组件的引入对晶态材料的结构和性能的影响规律。关键词：晶态材料配体构型配体长度空间位阻磁学性能发光性能AbstractEmbarkingfromtheapplicationsandfunctionalitiesofmaterials,eighteennovelmetal-organiccrystallinematerialswererationallydesignedbasedonaromaticdicarboxylicacidincombinationwithauxiliaryN-Donorligands.Theirsynthesisconditions,influencingfactors,topologystructureandopticalandmagneticpropertieswerediscussedinthispaper.Maincontentcanbedividedintothreepartssortedbydifferentligandsused.Thefirstpartistheinfluenceofligandconformationoncrystalstructures.Complex1~6weresynthetizedbasedon3,3-biphenyldicarboxylicacid,ofwhich1~3present1DchainsofdifferenttypepreparedincombinationwithchelateN-Donorligandsand4~6exhibit3DstructurepreparedincombinationwithbridgingN-Donorligands.Thesecondpartistheinfluenceofligandlengthoncrystalstructures.BytuningthelengthofN-Donorligands，twoseriesofMOFs（7~9and10~14）basedon2,4-biphenyldicarboxylicacidwereobtainedandthestructuraldimensionsofthoseMOFsgrowwiththeincreasinglengthofN-Donorligands.Thethirdpartistheinfluenceofsterichindranceoncrystalstructures.Complex15~18werepreparedwithmixeduseof9-fluorenone-2,7-dicarboxylicacidandN-Donorligands,wherechelateN-Donorligandsfor15~17andbridgeN-Donorligandsfor18.ThedispersionoftheirSBUsin15~17getincreasedwithvariedsterichindranceofchelateN-Donorligandsandcomparingto15~17,theintroductionofbridgeN-Donorligandleada3Dnetworkof18.Thesyntheses,structuresandpropertiesofthoseMOFsmentionedabovehavebeencharacterizedandanalyzedindetailandhowthecrystalstructure,andpropertieswereinfluencedbytheintroductionofN-donorswereemp