本文關(guān)鍵詞： 含1 2 4-triazole雜環(huán)的吡啶類配體 咪唑二羧酸類配體 氣體吸附　出處：《山東師范大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：金屬-有機(jī)框架(MOFs)和以配位驅(qū)動(dòng)的超分子化合物是目前化學(xué)界非常活躍的研究領(lǐng)域之一,不僅是因?yàn)槠渚哂形说慕Y(jié)構(gòu),而且還因?yàn)槠湓跉怏w吸附、分離、催化等領(lǐng)域具有很多潛在的應(yīng)用。本文合成了一系列含氮雜環(huán)配體,即含1,2,4-triazole雜環(huán)的吡啶類彎折型有機(jī)配體以及以氧化吡啶為端基的咪唑二羧酸類有機(jī)配體,并且研究了它們與過渡金屬、稀土金屬的配位反應(yīng)化學(xué),得到了16例結(jié)構(gòu)新穎的MOFs。本文利用X-射線單晶衍射、粉末衍射、紅外、熱重分析表征了它們的結(jié)構(gòu),并且著重研究了一例Ni(II)-MOF的物理化學(xué)性質(zhì)。I、合成了四例含1,2,4-triazole雜環(huán)的吡啶類彎折型有機(jī)配體L1-L4,研究了它們與過渡金屬(M=Co(II)、Ni(II)、Pb(II)、Cd(II)、Cu(II)、Zn(II))的配位化學(xué)反應(yīng),得到了10例未見報(bào)道的配位化合物,并對(duì)其單晶結(jié)構(gòu)進(jìn)行了分析。研究表明,金屬中心、平衡陰離子、有機(jī)配體的配位點(diǎn)和構(gòu)象的不同對(duì)配位化合物的拓?fù)浣Y(jié)構(gòu)具有直接的影響。另外還討論了π-π、C-H?O、C-H?N、C-H?π等弱相互作用對(duì)構(gòu)建穩(wěn)定化合物的作用。II、利用富含N原子的4-amino-1,2,4-triazole多齒有機(jī)配體L1(4-氨基-3,5-二[5’-(4,3’-聯(lián)吡啶基)]-1,2,4-三氮唑)與Ni(OAc)2在溶劑熱的條件下發(fā)生配位化學(xué)反應(yīng),合成了一例具有梭形隧道的三維Ni(II)-MOF,并且利用X-射線單晶衍射表征了它的結(jié)構(gòu)。研究表明該Ni(II)-MOF良好的熱穩(wěn)定性,化學(xué)穩(wěn)定性以及較高的比表面積使其成為吸附氣體小分子二氧化碳和甲烷的良好材料。III、合成了以氧化吡啶為端基的咪唑二羧酸類有機(jī)配體L5,研究了它與稀土金屬(M=La(III)、Ce(III)、Eu(III))的自組裝反應(yīng),得到5例未見文獻(xiàn)報(bào)道的化合物,并對(duì)其單晶結(jié)構(gòu)進(jìn)行了分析。研究表明輔助配體如甲酸和草酸對(duì)合成不同結(jié)構(gòu)的化合物具有重要的影響。
[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.
【學(xué)位授予單位】：山東師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4
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本文編號(hào)：1547553