Syntheses And Properties Of Transition Metal Complexes Constructed By 1,2,3-Benzenetricarboxylic Acid Derivatives

Coordination polymer can be defined as inorganic-organic hybrid materials in a broad sense,both of which have the characteristics of the metal complexes and organic polymer compounds.There are both good stability,rich structure and varied properties in coordination,Which have shown broad application prospect,such as adsorption separation,fluorescence induction,heterogeneous catalysis,new energy,and so on.However,the multidentate carboxylic acid not only have multiple coordination points and rich coordination patterns,which becomes the focus of researchers.In this paper,and with the introduction of nitrogen-containing auxiliary ligand,successfully synthesized three series of functional complexes.Under the auxiliary coordination of nitrogen containing ligands and transitional metals?Cu,Ag,Zn,Cd?,which are chosen to be central metal.Organic ligand used from four kinds of 1,2,3-benzenetricarboxylic acid derivatives?H₄BTEC=1,2,3,5-benzenetetra-carboxylic acid,H₃BITRC=3,4,5-biphenyltricarboxylic acid,H₅BIPEC=3,4,5,3',5'-biphenylpentacarboxylic acid,SH₄BTEC=5-Sulfo-1,2,3-benzenetricarboxylic acid?,nitrogen-containing auxiliary ligand be added in system.and 12 different dimensional metal-organic coordination polymers have been hydrothermally synthesized.And by studying the relationship between crystal structure and properties of complexes,this paper summarizes the rules of the system and an experimental foundation for the directional design and synthesis of functional complexes with novel topological structure and excellent properties.The results are as follows:1.Four novel copper coordination polymers constructed from H₄BTEC,namely,[Cu₇?BTEC?₂?OH?₆?H₂O?₆]·2NH₃?1?,[Cu₄?BTEC??OH?₄?2,2'-bpy?₄?H₂O?]·6H₂O?2?,[Cu₃?BTEC??OH?₂?bpy?_0.5?H₂O?₂]·4H₂O?3??4?have been synthesized with hydroth-ermal methods;The complexes 1,3,4 are composed of multinuclear clusters as secondary structural units,Although the complexes 3 and complexes 4 are isomers,the space group is different.the organic ligands as the frame-link bridge.Finally the three-dimensional porous complexes are formed.In the experiment process,by adjusting the reaction temperature,auxiliary ligand,pH value of solution,adding different anionic charge complexes topological network,constructing the functional complexes of different structures,and exploring the influence rule of reaction conditions on product structure and properties.The thermal stability,catalytic activity,gas adsorption performance and selective adsorption properties of the complexes were studied.2.A bi-functional porous complex[Cu₂?BIPEC??H₂O?₂]?5?with classical paddle-type secondary structure units was constructed by using H₅BIPEC and transition metal copper under solvothermal conditions The complex not only exhibits good activity in gas adsorption and catalytic silicon cyanide reaction,but also exhibits excellent selective adsorption ability for methylene blue dyes,Accumulating a good foundation for the study of selective adsorption of complexes.Three coordination complexes based on H₃BITRC,transition metals?Ag,Zn?and auxiliary ligand.namely,[Zn₃?BITRC?₂?H₂O?₂]·?bpy?_0.5?6?,[Zn₆?BITRC?₄?bpea??H₂O?₃?CH₃O-H?]?7?,[Ag₃?BITRC?]?8?.During the experiment,the effects of metal ions and auxiliary ligands on the structure and properties of the products were investigated.Three kinds of functional complexes were synthesized by adjusting the reaction temperature,pH value and other external factors.The thermal stability,fluorescence and catalytic activity of the complexes also were studied.3.Four transitional mental complexes[Cd₂?SBTEC??phen?₂?H₂O?₄]?9?,[Cd₂?SBTE-C??phen?₂?H₂O?]?10?,[Zn?bpy??H₂O?₄]·[Zn?SBTEC??bpy??H₂O?₂]·4H₂O?11?,[Cu₄-?SBTEC?₂?bpy?₂?H₂O?₄]?12?were synthesized through the reaction of Cd?II?,Zn?II?,and Cu?II?ions with SBTEC and auxiliary ligand.During the process,the effects of metal ions and ligands on the structure and properties of the product were investigated.The functional complexes with novel structure and various properties were designed by controlling external factors such as reaction temperature and solution pH,and their thermal stability,catalysis and fluorescent properties were studied.