基于ε-Keggin型多酸无机-有机杂化化合物的合成及其电化学性能的研究

发布时间：2018-04-14 04:32

  本文选题：多金属氧簇 + 无机-有机杂化材料　； 参考：《延边大学》2017年硕士论文

【摘要】：多金属氧酸盐也称多酸,是高氧化态的前过渡金属离子通过氧连接而成的一类多金属氧簇化合物。由于具有结构多样性和良好的性质,使其在诸多领域都展现出潜在的应用价值,例如磁性、医药、光化学、生物催化等领域。多酸和多酸之间可以通过M-O-M'键(M,M':过渡金属)相连。金属有机骨架(MOFs)也被称为多孔配位聚合物(PCPs),因其潜在可设计的拓扑结构和良好应用性能得到迅速发展。作为一个新型多孔材料,它的合成可以通过配位键连接金属节点(离子或集群)和有机桥连配体。由于结构和功能的可调性,使其在合成化学和材料科学领域中飞速发展。多酸可以作为重要的无机构筑单元与有机配体或金属有机配体相连合成新的有机-无机杂化化合物。有时这种多酸基配位聚合物被称为POMOFs。多酸基配位聚合物的研究已成为多酸化学发展的一个研究热门。本文以Zn-ε-Keggin为构筑单元,以二齿半刚性配体4'-(4-carboxyphenoxy)-[1,1'-biphenyl]-4-carboxylie(CPBPC)和三齿半刚性配体4,4',4"-((1,3,5-triazine-2,4,6-triyl)tris(azanediyl))tribenzoic acid)(TATAB)为桥联配体在水热条件下与氯化锌反应生成两例基于多酸的无机-有机杂化化合物。在合成过程中通过调节反应条件,例如溶液的pH值、反应温度和原料配比等,找到制备目标化合物的最佳反应条件,并对其性质进行表征。本文合成的化合物分别为:[TBA]3[PMov8MoⅥ4O36(OH)4Zn4][CPBPC]2(1)[TBA]3[PMov8MoⅥ4O36(OH)4Zn4][PTABAB][HPTABAB].7H20(2)(PTABAB4,4'-((6-(phenylamino)-1,3,5-triazine-2,4-diyl)bis(azanediyl))dibenzoate)。配体TATAB在反应过程中发生脱羧反应生成PTABAB。在晶体1中,Zn-ε-Keggin单元与配体CPBPC生成一种具有八层互穿的three-dimensional(3D)dia骨架结构,其可以理解成由2个四层互穿单元进一步互穿。晶体2具有two-dimensional(2D)层状结构,相邻层互穿形成双层,并且相邻的互传层以AAA序列排列。在单配体条件下,这是首例Zn-ε-Keggin单元上的锌离子具有两种不同类型几何配位的报道。同时对它们的电化学性能进行了测试。
[Abstract]:Polyoxometalates, also known as polyacids, are a class of polyoxometallic clusters formed by oxygen bonding of highly oxidized pretransition metal ions.Due to its diverse structure and good properties, it has shown potential applications in many fields, such as magnetism, medicine, photochemistry, biocatalysis and so on.Polyacids and polyacids can be connected by M-O-M 'bond MN: transition metal.Organometallic skeleton (MOF) is also known as porous coordination polymer (PCPs), which has been developed rapidly because of its potential design topology and good application properties.As a new porous material, its synthesis can connect metal nodes (ions or clusters) and organic bridging ligands by coordination bonds.Due to the tunability of structure and function, it has been developed rapidly in synthetic chemistry and material science.Polyacids can be used as important inorganic building units to link with organic ligands or metal-organic ligands to synthesize new organic-inorganic hybrid compounds.This polyacid coordination polymer is sometimes called POMOFs.The study of polyacid coordination polymers has become a hot topic in the development of polyacid chemistry.In this paper, Zn- 蔚 -Keggin is used as the building unit, and the bidentate semi-rigid ligand 4- (4-carboxyphenoxyoxy-4) -4 carboxylieate (CPBPC) and the tridentate semi-rigid ligand 4O4 "-triazine-246-triyltriazine-246-triyltriazine-246-triazine-246-triazine-246-triazine-2-triazine-246-triazine-triazine-246-triazine-triazine-triazine-246-triazine-triazine-triazine-246-triazine-trioxylbenzoic acidTATAB) are used as the bridged ligand to form two inorganic organic heteropolymers based on polyacid under hydrothermal conditions.By adjusting the reaction conditions, such as pH value of solution, reaction temperature and ratio of raw materials, the optimum reaction conditions for the preparation of the target compounds were found and their properties were characterized.The compounds synthesized in this paper are: [TBA] 3 [PMov8Mo 鈪，

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