多齿四氮唑配体构筑配合物的催化性能及中心金属离子交换的研究

发布时间：2018-02-02 15:10

本文关键词： 金属有机框架中心金属交换探针非均相催化　出处：《郑州大学》2017年硕士论文　论文类型：学位论文

【摘要】：金属有机框架(MOFs)材料具有结构的多孔性,高的比表面积,结构的可控性等特点,赋予其在发光、储能、催化等方面具有广泛的应用。其固定化的活性中心,可以实现高效的离子探针识别、有机反应催化。因此,为了进一步研究中心金属离子交换对其性能的影响,我们设计合成了非手性配体4,5-二-2H-四氮唑基-咪唑(L1),轴手性配体R-2,2-二乙基-1,1-联萘-4,4,6,6-四羧酸(L2)和R-2,2-二乙基-1,1-联萘-4,4,6,6-四-2H-四氮唑(L3)三个有机配体,通过水热法构筑了13个MOFs材料,并对其催化性能或光学性能做了详细的研究。本文主要分为两部分:1.利用配体L1作为连接配体构筑过渡金属锌和钴的配合物1-5,并对其结构做了详细的研究。荧光光谱表明Zn-MOF在作为发光材料有很好的应用前景。配合物1作为非均相催化剂在催化Nzarov串联环化反应合成环戊烯酮化合物的具有很好催化效果,并对其它配合物2-5的催化效果较差原因进行了分析。2.通过原料的手性拆分,酚基的保护,水解等合成步骤,设计合成含有手性配体L2和L3,作为联萘结构衍生物L2和L3配体与金属Cd,Cu构筑不同的配合物6-7。6可以与Cu,Co,Ni发生中心金属交换,实验证明符合Irving Williams序列。6的荧光性能比较好,在检测硝基芳香化合物探针的实验中,发现硝基化合物硝基的数目是影响其响应的重要条件。3.在设计配体里引入四苯乙烯发射团,构筑多了铜的配合物,其中配合物14是笼状结构,15是三维孔状结构,16是三维无孔洞结构。
[Abstract]:Organometallic frame (MOF) materials have the characteristics of porous structure, high specific surface area, controllable structure and so on, which endow them with luminescence and energy storage. The immobilized active sites can be used to identify highly efficient ion probes and catalyze organic reactions. Therefore, in order to further study the effect of metal ion exchange on its performance. We have designed and synthesized a non-chiral ligand 4o 5- 2H-tetrazolidazolyl-imidazolium L _ (1), and an axial chiral ligand R ~ (2 +) -diethyl-1- (1) -binaphthalene (BN) ~ (4N) 4O _ (6). Three organic ligands, 6-tetracarboxylic acid L _ 2) and R-2N _ 2-diethyl -1C _ 1-binaphthalene _ 4N _ 4N _ 4N _ 4, C _ (6) -4 ~ (-4) -4H _ (4) H _ (4) O _ (3). Thirteen MOFs materials were prepared by hydrothermal method. The catalytic and optical properties of the complexes were studied in detail. This paper is divided into two parts: 1. The ligand L1 is used as the ligand to construct the transition metal complexes 1-5 of zinc and cobalt. The structure of Zn-MOF is studied in detail. The fluorescence spectra show that Zn-MOF has a good application prospect as a luminescent material. Complex 1 is used as heterogeneous catalyst for the synthesis of Nzarov in series cyclization. Cyclopentenone compounds have good catalytic effect. The reasons for the poor catalytic performance of other complexes 2-5 were analyzed. 2. The chiral ligands L2 and L3 were designed and synthesized by chiral resolution, protection of phenolic groups, hydrolysis and other steps. As binaphthalene derivatives L _ 2 and L _ 3 ligands, different complexes 6-7.6 can be exchanged with Cu _ (2) Co _ (2) Ni. It was proved that the fluorescence properties of the probe which accord with the Williams sequence of Irving were better, and the detection of nitro-aromatic compound probe was carried out in the experiment. It is found that the number of nitro compounds is an important condition for its response. 3. Tetrastyrene emitters are introduced into the design ligands to construct copper-rich complexes, in which complex 14 is a cage structure. 15 is a three-dimensional porous structure and 16 is a three-dimensional void-free structure.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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