基于刚性咪唑类配体的金属有机框架的合成及性能研究

发布时间：2018-07-06 12:17

本文选题：金属有机框架 + 四苯乙烯　；参考：《西华师范大学》2017年硕士论文

【摘要】：金属有机框架由金属离子/集簇和有机配体构成,由于其多孔性、大的表面积和结构的可调等特性受到了科学家的广泛关注。另一方面金属有机框架结构的特点也决定了它在气体存储/吸附、催化、磁性、药物传递和传感等方面的应用。此外,荧光性的金属有机框架在发光检测/感应和光催化方面也受到了科学家的青睐。四苯乙烯由四个苯环和一个乙烯键组成,在固态时具有良好的荧光性能常作为一种很好的聚集诱导发光(AIE)材料。因此,我们基于四苯乙烯单元引入咪唑基团合成了刚性的四齿咪唑类有机配体四(4-咪唑基苯基)乙烯(TIPE)(L)并通过水热法和后合成法合成了五个新颖的金属有机框架1-5{[Cd_4(L)_2(OBBA)_4]·8H_2O}n(1)、{[Co_4(L)_2(BPDC)_4]·5MeCN·16H_2O}n(2)、{[Cu_4(L)3·5Cl}n(3)、{[Cd_4(L)_2]·2H_2O}n(4)和{[Co_4(L)_2(BPDC)_4]·2H_2O}n(5),利用PXRD、红外光谱、X射线单晶衍射、元素分析等手段对其结构进行表征。另外,我们还进行了气体吸附、荧光感应及催化性能的测试探索其潜在的应用价值。结果显示配合物1是一个三维四重穿插4-c afw网状结构,它的拓扑符号为{{3.75}{3.7.7.7.7(2).7(2)}。在配合物2中钴离子作为五链接节点而有机配体作为四链接节点整个结构是一个少见的三维和三维相互穿插的四重穿插4,4-c 4T67网状结构,用拓扑符号表示为{{4.64.8}2{42.62.82}。配合物3拥有罕见的[Cu_4Cl]~(3+)二级结构单元,有机配体链接二级结构单元整个结构形成一个三维穿插的sqc6网状结构它的拓扑符号为{66}{6(2).6(2).6(2).6(2).6(2).6(2)}。配合物4是蝴蝶结型的链状结构,链与链之间延伸形成一个二维结构。配合物5是一个三维穿插结构,整个结构中包含了两种不同大小的通道,它们的尺寸大小分别为23.2602(13)×15.974(12)?2和24.6324(15)×14.5478(12)?2。热稳定性能分析显示配合物1-4具有良好的热稳定性其分解温度都在300℃以上。固体荧光测试证明配合物1、3和4有良好的荧光性能,配合物1更是对硝基爆炸物及甲基苯丙胺有良好的感应效果。另外配合物4对1,3-偶极环化反应具有良好的催化效果,当反应时间为3 h反应温度为60℃时产率可以达到90%以上。卟啉及金属卟啉衍生物具有独特的物理、化学、电学性能以及在能量和电子转移、捕光、催化方面的特性,通过卟啉来构建功能性的金属有机框架受到了科研工作者的关注。基于此我们合成了5,10,15,20-四-(1,3-咪唑基)卟啉配体并在水热条件下得到了金属有机框架[Cd_3L_3Cl_3O_2]·solvent(6),X射线单晶衍射数据显示其结构为三斜p_1空间群。
[Abstract]:Metal organic frameworks are made up of metal ions / clusters and organic ligands. Due to their porous properties, large surface area and the adjustable structure, the characteristics of metal organic frame structure also determine its application in gas storage / adsorption, catalysis, magnetism, drug delivery and sensing. In addition, the fluorescent metallic organic frameworks are also favored by scientists in the field of luminescence detection / induction and photocatalysis. Four styrene is composed of four benzene rings and one ethylene bond, with good fluorescence properties in solid state as a good aggregation induced luminescent (AIE) material. Therefore, we introduce imidazole based on the four styrene unit. The group synthesized a rigid four diazolidic ligand four (4- imidazolyl phenyl) ethylene (TIPE) (L) and synthesized five novel metal organic frameworks 1-5{[Cd_4 (L) _2 (OBBA) _4]. 8H_2O}n (1), {[Co_4 (L) _2 (2), 3. (BPDC) _4]. 2H_2O}n (5), using PXRD, infrared spectrum, X ray single crystal diffraction, element analysis and other means to characterize its structure. In addition, we have also carried out gas adsorption, fluorescence induction and catalytic performance testing to explore its potential application value. Results show that complex 1 is a three-dimensional and four weight interspersed 4-C AFW network structure, its topology The symbol is {{3.75}{3.7.7.7.7 (2).7 (2)). In the complex 2 cobalt ion as the five link node and the organic ligand as the four link node the whole structure is a rare three-dimensional and three-dimensional interspersed four heavy 4,4-c 4T67 network structure, with the topology symbol expressed as the {{4.64.8}2{42.62.82}. complex 3 with a rare [Cu_4Cl]~ (3+) two. The structure unit, organic ligand links the two stage structure unit to form a three-dimensional and interspersed sqc6 network structure. Its topology symbol is {66}{6 (2).6 (2).6 (2).6 (2).6 (2).6 (2)). The complex 4 is a bow type chain structure, and the chain extends between the chain and the chain to form a two-dimensional structure. The complex 5 is a three-dimensional interspersed structure, the whole knot The structure contains two different sizes of channels, their size and size are 23.2602 (13) * 15.974 (12), 2 and 24.6324 (15) x 14.5478 (12)? 2., thermal stability analysis shows that the complex 1-4 has good thermal stability and its decomposition temperature is above 300. The solid fluorescence test proves that the complexes 1,3 and 4 have good fluorescence properties, fit together. The substance 1 has a good induction effect on nitro explosives and methamphetamine. In addition, the complex 4 has good catalytic effect on the 1,3- dipole cyclization reaction. When the reaction time is 3 h, the yield can reach more than 90%. Porphyrin and metalloporphyrin derivatives have unique physical, chemical, electrical properties and energy. The properties of electron transfer, light capture and catalysis have attracted the attention of researchers. Based on this, we synthesized the 5,10,15,20- four - (1,3- imidazolyl) porphyrin ligand and obtained the metal organic framework [Cd_3L_3Cl_3O_2]. Solvent (6), X ray single crystal diffraction data under the hydrothermal condition. It is shown that its structure is three oblique p_1 space group.
【学位授予单位】：西华师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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