【作者】 张鹏；

【导师】 郑昌戈；

【作者基本信息】 江南大学 ， 化学工艺， 2012， 硕士

【摘要】 作为功能固态材料,配位聚合物在光电、磁性、气体吸附、离子交换以及催化等方面具有卓越的性能,其设计与合成已引起人们的极大兴趣。合适的有机配体以及金属中心的选择,是设计与合成新型配位聚合物的关键所在。在合成配位聚合物的过程中,有机配体的结构特点、金属原子配位的几何构型、金属与配体的比例、溶剂体系以及氢键等诸多因素都有重要的影响。本论文设计合成了具有刚性结构的含羧基芳香族化合物3,3′,5,5′-苯基-1,3-二苯四羧酸作为构筑配位聚合物的有机配体。以3,5-二甲基溴苯为起始原料,经格式、氧化和酯化等反应,得到3,5-二羧酸二乙酯苯硼酸。通过与1,3-二溴苯的Suzuki偶联反应,再经水解得到目标产物3,3′,5,5′-苯基-1,3-二苯四羧酸,总转化率为30.8%。本论文还以3,3′,5,5′-苯基-1,3-二苯四羧酸、2,3,5,6-四氯对苯二甲酸、咪唑和1,1′-（1,4-丁基）二咪唑（bbi）为有机配体,选择Co2+、Ni2+以及Cu2+为过渡金属配位中心,采用扩散和挥发等方法合成得到4个金属有机配位聚合物[Co（tcbdc） （imidazole）₂（H₂O）₂] 1, [Co（bbi）₂（H₂O）₂]·（tcbdc）·2H₂O 2, [Ni（tcbdc）（bbi）（H₂O）₂]·2DMF 3 and [Cu2（bbi）4]·（pbtc）·15H₂O 4 （ bbi=1,1’-（1,4-butanediyl）bis（imidazole）, tcbdc=tetrachloro benzene-1,4-dicarboxylate, H4pbtc=3,3’,5,5’-benzene-1,3-triyl-tetrabenzoic acid）。通过X-射线单晶衍射、元素分析、红外光谱、热重等手段对其进行了结构与性能的研究,结果表明:1为一维链状结构,2为一维串珠形链,3和4为层状网络结构,且4具有2.6.6.6型拓扑结构。更多还原

【Abstract】 The design and synthesis of coordination polymers, as functional solid-state material, has attracted great interest, owing to their excellent properties in photoelectric, magnetism, gas storage, ion exchange and catalysis. Ligands and metal centers play an important role to design and synthesize novel coordination polymers. However, predicting the exact structures of coordination polymers is difficult. Many factors, such as the structural characteristic of the ligand, the coordination geometry of the central metal atoms, the ratio of metal and ligand, the solvent system and the H-bond, make important effect in the synthesis of the coordination polymers.With rigid structure of aromatic compounds, 3,3’,5,5’-benzene-1,3-triyl-tetrabenzoic acid （H4pbtc） was synthesized as key ligand to coordination polymers. Besides, （3,5-bis（ethoxycarbonyl）phenyl）boronic acid was also synthesized by Grignard reaction, oxidation reaction and esterification reaction. With 1-bromo-3,5-dimethylbenzene as the starting material, 3,3’,5,5’-benzene-1,3-triyl-tetrabenzoic acid was obtained by Suzuki coupling reaction of （3,5-bis（ethoxycarbonyl）phenyl）boronic acid and m-dibromobenzene. After hydrolyzation, the total yield is 30.8%.With 3,3’,5,5’-benzene-1,3-triyl-tetrabenzoic acid, tetrachlorobenzene-1-4-dicarboxylic acid, imidazole or 1,1’-（1,4-butanediyl）bis（imidazole） as ligands, [Co（tcbdc）（imidazole）₂ （H₂O）₂] 1, [Co（bbi）₂（H₂O）₂]·（tcbdc）·2H₂O 2, [Ni（tcbdc）（bbi）（H₂O）₂]·2DMF 3 and [Cu2（bbi）4]·（pbtc）·15H₂O 4 were obtained by diffusion or evaporation methods. Their structures were characterized by X-ray diffraction, elemental analysis, IR and thermogravimetric analysis. The result suggests that complexes 1, 2, 3 and 4 show the 1D chain, 1D double-stranded chain and both 2D network structures, respectively. The complex 4 has the topology of 2.6.6.6 net.更多还原