羧基苯氧乙酸金属配位聚合物的合成与结构化学研究
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摘要
配位聚合物已成为当前配位化学、超分子化学及材料和生命科学等
领域中的热点之一。目前羧酸配位聚合物的研究主要集中在如苯二甲
酸,均苯三甲酸等刚性芳香多羧酸配体。本论文设计合成了间(对)羧基
苯氧乙酸有机桥配体,采用自组装和水热法建构出18个具有双核大环、
一维链、层状和网状的羧基苯氧乙酸金属配合物,并对其进行了元素分
析、IR、荧光、热重和晶体结构表征。结果表明:羧基苯氧乙酸呈现出
双齿、三齿、四齿、五齿桥联配位方式及作为抗衡离子存在,配体的羧
基氧和醚氧原子均可配位成键,且具有较好的刚柔特性。此外,探究了
反应体系的pH值、溶剂、不同金属盐和氮杂环等条件因素对配合物的
合成与拓扑结构的影响。
Currently, the construction of the coordination polymers has become one of the particularly important and topical subjects in the fields of coordination chemistry, supramolecular chemistry, material and biological science et al. The current topical research focus on the rigid aromatic multicarboxylate ligands, such as benzene dicarboxylic acid and benzene tricarboxylic acid et al. In this thesis, two organic bridging carboxylate ligands, carboxylphenoxyacetic acids (3- and 4-CPOAH2), were designed and synthesized, and were used to construct eighteen coordination polymers with a great variety of topological structures, including binuclear macrocyclic, 1-D chain, 2-D layer as well as 3-D network, which were characterized by elemental analysis, IR, TG, PL and X-ray single crystal diffraction. In these polymers, the 3- and 4-CPOA~(2-) ligands, which are excellent bridging characteristic with both rigid and flexible parts, act in a counter-ion or show multiple coordination modes through carboxylate O or ether O atoms. In addition, the effects of pH value, solvents, metal salts and nitrogen heterocycle molecules on the synthesis and topological structures of the coordination polymers have also been studied.
领域中的热点之一。目前羧酸配位聚合物的研究主要集中在如苯二甲
酸,均苯三甲酸等刚性芳香多羧酸配体。本论文设计合成了间(对)羧基
苯氧乙酸有机桥配体,采用自组装和水热法建构出18个具有双核大环、
一维链、层状和网状的羧基苯氧乙酸金属配合物,并对其进行了元素分
析、IR、荧光、热重和晶体结构表征。结果表明:羧基苯氧乙酸呈现出
双齿、三齿、四齿、五齿桥联配位方式及作为抗衡离子存在,配体的羧
基氧和醚氧原子均可配位成键,且具有较好的刚柔特性。此外,探究了
反应体系的pH值、溶剂、不同金属盐和氮杂环等条件因素对配合物的
合成与拓扑结构的影响。
Currently, the construction of the coordination polymers has become one of the particularly important and topical subjects in the fields of coordination chemistry, supramolecular chemistry, material and biological science et al. The current topical research focus on the rigid aromatic multicarboxylate ligands, such as benzene dicarboxylic acid and benzene tricarboxylic acid et al. In this thesis, two organic bridging carboxylate ligands, carboxylphenoxyacetic acids (3- and 4-CPOAH2), were designed and synthesized, and were used to construct eighteen coordination polymers with a great variety of topological structures, including binuclear macrocyclic, 1-D chain, 2-D layer as well as 3-D network, which were characterized by elemental analysis, IR, TG, PL and X-ray single crystal diffraction. In these polymers, the 3- and 4-CPOA~(2-) ligands, which are excellent bridging characteristic with both rigid and flexible parts, act in a counter-ion or show multiple coordination modes through carboxylate O or ether O atoms. In addition, the effects of pH value, solvents, metal salts and nitrogen heterocycle molecules on the synthesis and topological structures of the coordination polymers have also been studied.
引文
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