Design, Synthesis, Crystal Structure And Properties Of Metal-organic Coordination Polymers Constructed From Ru-pyridine Dicarhoxylic Complexes

In recent years, designing and constructing coordination polymers from organicligands and metal ions has become an attractive and promising research field not onlybecause of their topologically interesting architectures but also due to their potentialapplications in optics materials, gas storage and separation, magnetism, magneticmaterials, nanomaterials, catalysis,drug delivery and so on.And the Ru (Ⅱ)complexes with pyridine have many excellent properties in photochemical,electrochemical and biological chemistry and so on. They are, however, became astudy hotspot of scientific workers for a long time.In this thesis three diffirentmetalloligands are synthesized by the two kinds of organic ligand,2,2′-bipyridine-4,4′-dicarboxylic acid and2,2′-bipyridine-5,5′-dicarboxylic acid,react with the Ruion respectively. Seven novel mental organic frameworks (MOFs) are obtained byutilizing these metalloligands and the transition metal ions under solvothermalconditions. This paper utilize the measurements such as the single-crystal X-raydiffraction, the X-ray power diffraction, the IR measurement, the thermo-gravimetricanalysis and the fluorescent analysis and so on to character the new compounds andfocuce on the study of the MOFs used in the photocatalytic reduction of CO2reation.The main work can be divided into three parts:Firstly, we have synthesized the metalloligand1by the means of coordinating theorganic ligand2,2′-bipyridine-4,4′-dicarboxylic acid to Ru ion. Base on themetalloligand1, this part use the2,2′-pyridine as the second mixed ligand, andtransition metal ion Cd (Ⅱ) to obtained the metal organic coordinate polymer MOF1.The fluorescence property of MOF1reveals that the maximum emission wavelengthof MOF1is630nm, and the wide range of the light absorption wavelength from200to600nm makes it the potential photocatalytic material. The experiment ofphotocatalytic CO2reduction has been provided it.Secondly, we choose2,2′-bipyridine-5,5′-dicarboxylic acid and the Ru ion toconstruct the metalloligand2. Based on this ligand2, and transition metal ions Cd(Ⅱ)、Cu (Ⅱ)、Zn(Ⅱ) to obtained three new metal organic coordinate polymersMOF2-MOF4. The single crystal structure and the other basic properties wereanalyzed. The photocatalatic properties have also been attempted according to theexperiment of photocatalytic CO2reduction. Currently, The nano scale of MOF2andMOF3have been prepared successfully which is useful for further study. Finally, we choose2,2′-bipyridine-4,4′-dicarboxylic acid as the organic ligandand also coordinate with the Ru ion to construct the metalloligand3. MOF5issynthesized by the metallolgand3and the Cd (Ⅱ) under solvothermal conditions.And MOF5is three-dimensional dinuclear cluster microporosity polymer. In addition,applying for the solvothermal method the organic ligand2,2′-bipyridine-4,4′-dicarboxylic acid, Ru ion and the Co(CH3COO)2or Ni(CH3COO)2were added to thereactor, and the two allomerism metal organic coordinat polymers MOF6、MOF7were synthesized. The single-crystal data of MOF5and MOF6were analyzed, and theX-ray power diffraction proved that MOF6and MOF7is the isomorphism structure.The nano scale of MOF5has been prepared successfully and investigatedpotocatalytic property in the photocatalytic CO2reduction.