Synthesis, Structure And Properties Of Coordination Polymers Based On Bentdicarboxylate And Its Derivatives

As molecular based functional material, coordination polymer material whichthe topology structure and micro size can be adjusted, has widely application prospectin the fields of gas adsorption or separation, chiral catalysis or separation, drugdelivery, optical, electrical, magnetic. Design and synthesis of novel topologiesstructure and function of metal organic coordination polymers has become one of theresearch focus in the field of inorganic chemistry. As everyone knows, the structurecharacteristics of metal organic coordination polymers, especially its pore size, affecttheir chemical properties. And many other factors, such as metal ions, organic ligand,solvent, temperature, pH value, make the directional synthesis with a specificstructure size or properties of metal organic coordination polymers remains a greatchallenge. Modification of organic ligands using the functional groups with specificfunctions, making the desigen of synthesis of metal organic coordination polymermaterial with specific functional, has the widespread application.In this paper, we follow the principle of crystal engineering, different series ofpolycarboxylic acid organic ligands were designed and synthesized, metal organiccoordination polymers were synthesized with different solvents and second auxiliaryligand and its structure and properties were studied.We studied and discussed theinfluence factors about the structure of the polymer, such as metal ions, solventcomposition, length of second ligands are explored research. At the same time, weuse the method of functional modification, directional modification of organic ligand,metal organic coordination polymer with photocatalytic properties was synthesized,the catalytic efficiency and the factors which may affect its catalytic efficiency areanalyzed. The main results are as follows:(1) Based on the5,5’-oxydiisophthalic acid (H4odip), six new metal-organic frameworks (MOFs), Co2O(odip)(py)2(DMSO)2·3H2O (1),Co2(odip)(H2O)(DMA)2·2DMA (2), Co4(odip)2(H2O)4(DMSO)2·5DMSO (3),[Zn2(odip)(DMF)2(H2O)]·2DMF·2H2O (4), Zn2(odip)(H2O)(5) and In(odip)·3ACN(6), have been synthesized under solvothermal conditions. These six compounds werecharacterized by single-crystal X-ray diffraction, power X-ray diffraction and relativephysical methods. MOFs1,2and3are constructed from the same ligand andmetal-salt under the same temperature, but with different solvent, and they exhibitthree different topologies. MOF1possesses a3D4-coordinated architecture with(65·8) topology. MOF2features a3D4-coordinated net with (42·63·8) topology andMOF3shows a3D4-coordinated framework with (4·64·8)(4·65) topology. MOFs4and6have the same topology as MOF2. MOF5exhibits a3D5-coordinatedframework with (44·66) topology. These results indicate that the solvent environmentplays important roles in the formation of the final framework. Moreover, thephotoluminescence properties of4and5, and the magnetic properties of1,2and3have been studied and discussed.(2) Based on the bending type three carboxylic acid organic ligand H3cpbda((4,4’-(5-carboxy-1,3-phenylene)bis(oxy)dibenzoic acid), six metal organicframework compound: Zn(2,2’-bipy)(cpbda)(7), Zn2(4,4’-bipy)(cpbda)2(8),Zn5(H2O)3(cpbda)2·2DMF·2H2O (9), Cd3(4,4’-bipy)(cpbda)2(10),Mn3(cpbda)2(DMF)2(11) and Ln(cpbda)(H2O)(12) were synthesized undersolvothermal conditions with different length of the size of the second auxiliaryligand. The results show that, the topological structure of compound7-9exhibitedfrom the one-dimensional chain structure to the three-dimensional network structure,different with second auxiliary ligand. MOFs7is a one-dimensional chain structure,MOFs8is a two-dimensional layered structure, and MOFs9is a3D networkstructures. MOFs10and11were also the three-dimensional network structure. MOFs12also was a three-dimensional network structure, and has the same coordinationmode. In addition, the fluorescence properties of MOFs12with Eu and Tb andmagnetic properties of MOFs12with Dy, Gd and Ho were discussed. （3）Based on the5,5’-(1,2,3-triazole-1,4-diyl)diisophthalic acid (H4ctdipa),four new (MOFs), Cd2(ctdipa)(DMF)3·DMF(13), Cd4(ctdipa)2(H2O)(DMF)5(14),Mn2(ctdipa)(DMF)3(15), and Mn2(ctdipa)(H2O)2(DMA)·DMA(16), have beensynthesized under solvothermal conditions. These four compounds werecharacterized by single-crystal X-ray diffraction, power X-ray diffraction and relativephysical methods. MOF13possesses a3D4-coordinated architecture with (4·65)topology. MOF14features a3D4-coordinated net with (42·84) topology and MOF15shows a3D4-coordinated framework with (42·84) topology with the same topologyof MOF14. MOF16exhibits a3D4-coordinated framework with (42·65·8) topology.Moreover, the magnetic properties of15and16have been studied and discussed.(4) The rigid ligands of H2bpydc (4,4’-([2,2’-bipyridine]-5,5’-diyl)dibenzoicacid) was synthesized. By modifying Re metal group which having the function ofphotocatalytic to the organic ligand, the metal organic coordination polymer of{Zr6(O)4(OH)4[Re (CO)3Cl(bpydc)]6}·45DMF·5(TFA·DMA)(17) was synthesizedwith the same structure of UiO-66. The structure and properties of the compoundswere characterized. The results show that the MOFs17, can selective catalyticreduction the carbon dioxide to carbon monoxide, and photocatalytic decompositionof hydrogen generation with the ultraviolet irradiation conditions, and the acetonitrileas solvent, adding triethylamine. Sample was recovery after photocatalytic and MOFs17still has a high catalytic efficiency, which show the MOFs17has potentialapplication in heterogeneous photocatalysis.In summary, we study the influence of metal organic coordination polymerstructure and properties such as metal ion, reaction solvent, the second ligand, organicligand modification and others using solvothermal method. The MOFs1-17weresynthesized, provide a certain experimental for exploring the structure of MOFs. Atthe same time, the fluorescent, magnetic and photocatalytic properties are explored.