Synthesis And Properties Of Coordination Polymers Based On Flexible-Rigid Polycarboxylic Acid

MOFs materials with controlled aperture, diversity structures and functionalization has potentialapplication in gas storage, molecular recognization, microporous device, optics and magnetism. And it hasbecome one of the frontier research topics based on the synthesis of flexible-rigid combination ofcarboxylic acid and the research of the properties of MOFs materials.In this paper, we successfully synthesized series of coordination polymers with three dimensionalstructure by choosing three kinds of combination of flexible-rigid carboxylic acid ligands and metal ions,according to the principle of crystal engineering by the use of hydrothermal and solvent methods. And thenwe regulated and charactered the complexes by X-ray single crystal diffraction analysis, infrared spectra,element analysis, thermogravimetric analysis, X-ray powder diffraction in order to Study the fluorescenceproperties and magnetic of the kind of MOFs. After the experiments, we preliminarily summarized thesynthesis method and spatial structure regulation of the flexible-rigid combination of carboxylic acidMOFs materials.In this paper, there were five chapters. The first chapter was introduction, which was systematicallysummaried the basic concepts, the research present situation at home and aboard, selected topicbackground the topic of carboxylic acid type of MOFs materials application and synthetic methods offlexible-rigid combination of carboxylic acid MOFs materials. The second, the third and the fourth chapterwere mainly presented the synthesis characterization and property research of some kind of flexible-rigidcombination of carboxylic acid MOFs materials.In the second chapter, we maily synthesized H₂pdad organic carboxylic acid ligands by thehydrothermal and solvent methods, and then introduced the secondary building units4,4’ dipyridine tosynthsize four kind of MOFs materials, which were divided as follows: rare earth metal MOFs:[Ce（pdad）₂H₂O]·0.5H₂O （1）,[Nd（pdad）₂H₂O]·0.5H₂O （2）;[Sm（pdad）₂H₂O]·0.5H₂O （3）; transition metal:[Zn（pdad）（bpy）（H₂O）₂]_n（4）,[CoCl4（H₂O）₂]·pdad （5）. They were characterized by infrared spectroscopy,X-ray single crytal diffraction. MOF1,2, and3were isomorphous with microporous crystal structure. The recognition performance of MOF1and4with common transition metal ion was investigated byfluorescence spectrum and the magnetic of MOFs1and2were determined.In the third chapter, we described the structure and properties of seven crytal with H₃NTA ascarboxylic acid ligands, and the configuration of six crytal was isomorphous. These complexes were asfollows:[Ho（NTA）（H₂O）]_n（6）；[Dy（NTA）（H₂O）]_n（7）；[Sm （NTA）（H₂O）]_n（8）；[Nd（NTA）（H₂O）]_n（9）；[Er（NTA）（H₂O）]_n；（10）；[Gd（NTA）（H₂O）]_n（11）；{[Pr（NTA）（H₂O）]·2H₂O}_n（12）. The MOF6-11hadmicro holes and spiral structure. Fluorescence and thermodynamic properties of the MOFs materials werestudied, and the magnetism property of MOFs6,8, and12were determined.In the fourth chapter, we synthesized four kind of MOFs and a compound crytal using H4bptc, phen,bpy and transition metal ions by hydrothermal method, including [Mn2（bptc）₂（phen）·2H₂O]∞（13）；[Zn（bpy）（bptc）]·（H₂O）（14）；{[Zn2（bptc）4（bpy）₂] bpy}∞（15）；[Cu2（bptc）（bpy）₂]·2H₂O （16）；[（bptc）（bpy）H₂O]_n（17）, which were characterized by magnetism, fluorescence spectrum andthermogravimetric analysis. The microporous structure of MOF13and14were relatively clear, and theclass respiratory experiments of MOF15and16showed that they were the second generation of MOFsmaterials.The fifth chapter was the summary of the paper.