Synthesis, Structure And Properties Of Semi-rigid Aromatic Carboxylic Acid Ligands And Their Transition Metal Coordination Polymers

The design and construction of new functional coordination polymers have been one of the most intensive research topic in coordination chemistry, supramolecular chemistry and crystal engineering due to their novel topological structures and potential applications in the optical, magnetism, molecular recognition, gas storage, sensor and catalytic fields. So it is still a great challenge to synthesize coordination polymers with predictable structures and properties through the selection of reaction pathways. It is well known that the structures and properties of the MOFs are mainly dependent on two facts, organic ligands and metal atoms, which are main constructing elements of MOFs. The reaction conditions used also usually result in completely different framework structures in the assemble process of complexes. The dissertation is aimed to synthesize functional coordination polymers by the reaction of transition metal ions with four kinds of semi-rigid aromatic carboxylic acids. Three series,26 transition coordination polymers are designed and constructed. All coordination polymers are characterized by elemental analyses, IR spectra, X-ray single crystal diffraction, thermal gravimetric analyses, and their luminescence, magnetism and gas absorption is investigated. This dissertation includes the following four chapters:(1) The Chapter 1:The brief history of coordination chemistry and the basic concepts, principles, main synthetic methods, influence factors and application prospect of coordination polymer are simply introduced. Reviews on the research development of complexes containing of the benzene carboxylic acid and pyridine-carboxylic acid related with this dissertation were also briefly depicted.(2) The Chapter 2:H3TCBPA and H4BTTB were designed and prepared. And two new 3D microporous coordination polymer was constructed by the ligands and Cd2+under solvothermal condition. Single crystal X-ray diffraction analysis indicates that compound 1 and 2 display 2D?3D interpenetrated network containing 1D channel and two-fold interpenetrating three-dimensional framework structure, respectively. Furthermore, photoluminescence property, metal ion sensor and adsorption of 1 and 2 were also investigated.(3) The Chapter 3:Nineteen novel transition metal coordination polymers based on 4'-carboxy-4,2':6',4"-terpyridine (Hctpy), dicarboxylic acid auxiliary ligands and divalent metal salts (Zn2-?Cd2+?Co2+?Ni2+?Mn2+) have been synthesized successfully by changing temperature and solvent under hydro(solvo)thermal reaction. Complexes 3-21 show different framework structure, such as 1D(15,21),2D(4,5,7,8,10,11) and 3D(3,6,9,13, 14,16-20). All compounds were characterized by single-crystal X-ray diffraction, IR, XRD, and thermogravimetric analysis. Moreover, their photoluminescent, magnetism and sorption properties were also investigated. More importantly, compound 16 which exhibits a 3D porous MOF with Lewis basic sites, such as pyridyl sites, has been successfully applied in the detection of Fe3+ ions in DMF solutions and nitrobenzene and the probable detecting mechanism was also discussed.(4) The Chapter 4:Five novel transition metal coordination polymers based on 4'-(4-carboxyphenyl)-4,2':6',4"-terpyridine (Hctpy), auxiliary ligands containing N, O and metal salts (Zn2+?Cd2+?Co2+) have been synthesized successfully under hydro(solvo)thermal reaction. In self-assemble process of coordination polymer, we found that the introduction of auxiliary ligands, configuration of ligand and metal ion of reaction system have influence on controlling the structures and property of compounds 22-26. Moreover, their photoluminescent and magnetic properties were also investigated. Interestingly, compound 22, as a kind of excellent fluorescent sensor material, shows highly selective and sensitive response to acetone and Cu2+through luminescence quenching effects, making it a promising luminescent sensor for acetone molecule and Cu2+. The successful synthesis of these compounds may provide some useful information on synthesize new compounds based on Hcptpy ligand.