Construction Of Amino-functionalized Transition Metal Coordination Polymers And Fluorescence Sensing Properties

Due to the outstanding fluorescence characteristics and structural tunability,fluorescent coordination polymers（LCPs）play a very important role in the field of sensing detection and are favored by more and more researchers.In this thesis,anthracene,carbazole and fluorene with the rigidπ-conjugated structure and high fluorescence intensity were selected as the primitive,and different nitrogen-containing heterocyclic building units were obtained with imidazole and benzimidazole as the main body.In addition,linear amino-functionalized and V-type aromatic carboxylic acids were used as auxiliary ligands,and nine transition metal coordination polymers（CPs）were successfully constructed by solvothermal method by using mixed ligand strategy.The structure and properties of transition metal coordination polymers were characterized by X-ray single crystal diffraction,FT-IR,PXRD,TG and fluorescence,and the fluorescence sensing properties and chemical stability of partial coordination polymers were emphatically studied.The quenching mechanism was analized by experiment and theoretical calculation,and the main research contents are as follows:1.With anthracene as the primitive,flexible methylene and methylimidazole groups with hydrophobic effect were introduced to synthesize9,10-bis（（2-methyl-1H-imidazol-1-yl）methyl）anthracene（bmima）.In addition,2-aminoterephthalic acid（H₂atp）,[1,1’-biphenyl]-4,4’-dicarboxylic acid（H₂bpdc）and4,4’-diphenyl ether dicarboxylic acid（H₂oda）were selected as auxiliary ligands,and five transition metal coordination polymers with novel structures were synthesized by using the mixed ligand strategy.The topological analysis results show that CP 1belongs to a three-dimensional（3-c）（4-c）2-nodal topology,CP 2 can be simplified to a two-dimensional 4-c uninodal topology,CP 3 has an unusual three-dimensional five-fold interpenetrating 4-c uninodal dia topology,CP 4 and 5 are isomorphs,presenting a three-dimensional 6-c uninodal pcu topology.Fluorescence test shows that CP 1 and 3 can selectively identify Fe³⁺,Cr₂O₇^2-and TNP in water by fluorescence quenching,and have strong anti-interference ability and low detection limit,which can be used as better fluorescence sensing materials.2.With carbazole as the primitive,rigid benzimidazole groups were introduced to synthesize 3,6-bis（1H-benzo[d]imidazol-1-yl）-9-methyl-9H-carbazole（bbimc）.In addition,2-aminoterephthalic acid（H₂atp）and[1,1’-biphenyl]-4,4’-dicarboxylic acid（H₂bpdc）were used as auxiliary ligands,and two novel transition metal coordination polymers were synthesized.The topological analysis results show that CP 6 belongs to a two-dimensional 4-c uninodal topology,and CP 7 can be simplified to a three-dimensional double-interspersed 4-c uninodal topology.CP 6 shows good thermal and excellent acid/base stability in the aqueous solutions,Furthermore.CP 6can selectively identify Hg²⁺,CTC and TC in water by fluorescence quenching,and has the characteristics of fast response speed and good chemical stability.3.With fluorene as the primitive,benzimidazole and imidazole groups were introduced to synthesize 2,7-bis（1H-benzimidazol-1-yl）-9,9-dimethyl-9H-fluorene（bbdf）and 2,7-bis（1H-imidazol-1-yl）-9,9-dimethyl-9H-fluorene（bidf）.In addition,2-aminoterephthalic acid（H₂atp）was used as auxiliary ligands,and two novel transition metal coordination polymers were synthesized.The topological analysis results show that CP 8 belongs to the 4-c uninodal sql topology of three-dimensional double interpenetration,and CP 9 is a 4-c uninodal topology of three-dimensional quadruple interpenetration.CP 8 can selectively identify Hg²⁺,NFZ and NFT in water by fluorescence quenching,and has the characteristics of high selectivity and sensitivity.