以含氮杂环配体构建的MOFs的合成及吸附性质研究

发布时间：2018-02-28 13:47

  本文关键词： 含1 2 4-triazole杂环的吡啶类配体 咪唑二羧酸类配体 气体吸附　出处：《山东师范大学》2017年硕士论文　论文类型：学位论文

【摘要】：金属-有机框架(MOFs)和以配位驱动的超分子化合物是目前化学界非常活跃的研究领域之一,不仅是因为其具有吸引人的结构,而且还因为其在气体吸附、分离、催化等领域具有很多潜在的应用。本文合成了一系列含氮杂环配体,即含1,2,4-triazole杂环的吡啶类弯折型有机配体以及以氧化吡啶为端基的咪唑二羧酸类有机配体,并且研究了它们与过渡金属、稀土金属的配位反应化学,得到了16例结构新颖的MOFs。本文利用X-射线单晶衍射、粉末衍射、红外、热重分析表征了它们的结构,并且着重研究了一例Ni(II)-MOF的物理化学性质。I、合成了四例含1,2,4-triazole杂环的吡啶类弯折型有机配体L1-L4,研究了它们与过渡金属(M=Co(II)、Ni(II)、Pb(II)、Cd(II)、Cu(II)、Zn(II))的配位化学反应,得到了10例未见报道的配位化合物,并对其单晶结构进行了分析。研究表明,金属中心、平衡阴离子、有机配体的配位点和构象的不同对配位化合物的拓扑结构具有直接的影响。另外还讨论了π-π、C-H?O、C-H?N、C-H?π等弱相互作用对构建稳定化合物的作用。II、利用富含N原子的4-amino-1,2,4-triazole多齿有机配体L1(4-氨基-3,5-二[5’-(4,3’-联吡啶基)]-1,2,4-三氮唑)与Ni(OAc)2在溶剂热的条件下发生配位化学反应,合成了一例具有梭形隧道的三维Ni(II)-MOF,并且利用X-射线单晶衍射表征了它的结构。研究表明该Ni(II)-MOF良好的热稳定性,化学稳定性以及较高的比表面积使其成为吸附气体小分子二氧化碳和甲烷的良好材料。III、合成了以氧化吡啶为端基的咪唑二羧酸类有机配体L5,研究了它与稀土金属(M=La(III)、Ce(III)、Eu(III))的自组装反应,得到5例未见文献报道的化合物,并对其单晶结构进行了分析。研究表明辅助配体如甲酸和草酸对合成不同结构的化合物具有重要的影响。
[Abstract]:Metal-organic frameworks (MOFs) and coordination driven supramolecular compounds are currently one of the most active areas of research in the chemical world, not only because of their attractive structure, but also because of their adsorption and separation in gases. In this paper, a series of nitrogen-containing heterocyclic ligands have been synthesized, that is, pyridine bended organic ligands containing 1H 24-triazole heterocycles and imidazole dicarboxylic acid organic ligands with pyridine oxide as the terminal group. The coordination chemistry of them with transition metal and rare earth metal has been studied. Sixteen cases of MOFs with novel structure have been obtained. Their structures have been characterized by X-ray single crystal diffraction, powder diffraction, infrared and thermogravimetric analysis. The physicochemical properties of one case of Ni(II)-MOF, I., and the synthesis of four bended pyridine organic ligands, L1-L4, containing 1H 2N 4-triazole heterocyclic compounds, were studied. The coordination reactions between them and the transition metal transition metal (MCoC) were studied. Ten unreported coordination compounds were obtained. The results show that the coordination points and conformation of organic ligands have a direct effect on the topological structure of the coordination compounds. OFC-H? Nu C-H? The effect of 蟺 -weak interaction on the construction of stable compounds. II, the coordination reaction between 4-amino-1na-24-triazole and Ni(OAc)2 under solvothermal conditions was carried out using the N-rich polydentate organic ligand L _ (1) -4- (amino) -3N _ (5) bis ((5 ~ ((1)) ~ (-) ~ (-) ~ (-) ~ ((3)) -pyridyl)] -1 ~ (2 +) ~ (2 +) ~ (2 +) -triazol) under solvothermal conditions. An example of a three dimensional NiOII / MOF with fusiform tunnel was synthesized and its structure was characterized by X-ray single crystal diffraction. The results show that the Ni(II)-MOF has good thermal stability. Chemical stability and high specific surface area make it a good material for the adsorption of small gas carbon dioxide and methane. The imidazole dicarboxylic acid organic ligand L5 with pyridine oxide as the terminal group was synthesized and studied with rare earth metals. The self-assembly reaction of the Erythroid (Erythylum) is a kind of self-assembly reaction, which is characterized by the self-assembly reaction of the two species. Five unreported compounds were obtained and their single crystal structures were analyzed. The results show that the auxiliary ligands such as formic acid and oxalic acid play an important role in the synthesis of compounds with different structures.
【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：1547553