基于氧化吡啶、苯并咪唑类有机配体的配位聚合物的合成及性质研究

发布时间：2018-05-15 20:03

  本文选题：氧化吡啶 + 异相催化　； 参考：《山东师范大学》2017年硕士论文

【摘要】：配位聚合物的合成与性质研究是目前自组装化学领域的研究热点。超分子自组装是分子通过分子间相互作用自行聚集,形成有序结构的聚集体现象,它往往表现出单个分子或低级分子聚集体所不具有的特性与功能。在本文中,我们设计合成了一系列氧化吡啶配体、苯并咪唑配体,并将其与过渡金属进行自组装,都得到了13例结构新颖,性质优良的配位聚合物,利用粉末衍射、X-射线单晶衍射、红外及热重进行表征,并对其中具有代表性的配位聚合物进行了催化性质的研究。Ⅰ.利用本研究组内原有的两例以吡啶为端基的氧化吡啶桥连有机配体,将其与过渡金属进行自组装,得到了5例结构新颖的配位聚合物。其中有4例配位聚合物中氧化吡啶集团上的氧原子没有与金属发生配位,因此利用氧化吡啶Lewis碱的性质来催化Knoevenagel缩合反应。作为异相催化剂,其可被重复利用5次,有着较高的催化效率和选择性。Ⅱ将羧酸基团引入到氧化吡啶类有机配体中,在溶剂热的条件下,与过渡金属进行自组装,得到了4例结构新颖且稳定的配位聚合物,将参与配位的溶剂DMF分子与其他功能化的小分子交换,期待其用于氨基酸的识别。Ⅲ设计合成一系列苯并咪唑类的有机配体,与过渡金属自组装之后,得到了4例结构新颖的配位聚合物。在自组装的过程中,配体发生了碳碳键的断裂,并证明碳碳键断裂之后的产物。
[Abstract]:The synthesis and properties of coordination polymers are the focus in the field of self-assembly chemistry. Supramolecular self-assembly is a kind of aggregation phenomenon in which molecules gather by themselves through intermolecular interaction to form an ordered structure. It often shows the characteristics and functions that a single molecule or a low molecular aggregate does not have. In this paper, a series of pyridine oxide ligands and benzimidazole ligands were designed and synthesized, which were self-assembled with transition metals. X-ray single crystal diffraction (XRD), infrared spectroscopy (IR) and thermogravimetry (TGA) were used to characterize the coordination polymers, and their catalytic properties were studied. Two pyridine oxide bridged organic ligands with pyridine as terminal group were used in this study to self-assemble with transition metals, and five novel coordination polymers were obtained. In four of the coordination polymers, the oxygen atoms on the pyridine oxide group did not coordinate with the metal, so the properties of the pyridine oxide Lewis base were used to catalyze the condensation of Knoevenagel. As a heterogeneous catalyst, it can be reused for 5 times, and has high catalytic efficiency and selectivity. II the carboxylic acid group is introduced into the organic ligand of pyridine oxide and self-assembled with transition metal under solvothermal conditions. Four novel and stable coordination polymers were obtained. The solvent DMF molecules involved in the coordination were exchanged with other functionalized small molecules, which were expected to be used in the recognition of amino acids. III. A series of benzimidazole organic ligands were designed and synthesized. After self-assembly with transition metal, four novel coordination polymers were obtained. In the process of self-assembly, the ligand had the rupture of carbon and carbon bond, and it was proved that the product after the breaking of carbon and carbon bond.
【学位授予单位】：山东师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
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本文编号：1893728