芳香多羧酸配位聚合物的合成、结构与性质研究

发布时间：2018-06-03 11:23

本文选题：2 + 4(2　；参考：《长春工业大学》2017年硕士论文

【摘要】：金属-多羧酸配体的配位化合物结构新颖独特、变化多端,其次,它的潜在应用研究价值广泛巨大,比如吸附,磁性,荧光,电化学,催化等;除此之外,多羧酸配体的配位方式较之其他配体多种多样,配位能力也强很多,很容易配位组装出具有新颖独特结构和特异功能的配位化合物。因此这一类配合物的设计合成构筑和性质的研究长期受到研究人员的广泛关注。多金属氧酸盐作为一种综合方面都比较优异的无机金属氧簇,与有机配体结合杂化形成配合物时会有很多意外的惊喜作用,以多金属氧酸盐为基能够构筑一类结构新颖特异和潜在性能优异的化合物。近些年来,随着配位化合物的研究与深入,金属-有机配位聚合物的设计合成随着聚合物(离子热法、水热法和溶剂热等)合成方法的普遍应用,设计的合理性和实际应用性正在逐步的提高。本篇论文通过以Zn(II)为中心离子,2,4-二苯甲酰基间苯二甲酸和2,5-二苯甲酰基对苯二甲酸为主配体,引入不同的含氮配体,在不同的反应条件下,设计合成了2个结构独特的金属-有机配位聚合物,并对配合物进行了晶体结构分析,元素分析,IR表征和TGA分析,并对荧光进行了研究,结果如下:1、以2,4-二苯甲酰基间苯二甲酸(H_2L~1),2,5-二苯甲酰基对苯二甲酸(H2L2)为主配体,选择柔性含氮配体1,3-双(1,2,4-三唑-1-甲基)苯为辅助配体(1,3-bis(1,2,4-triazol-1-ylmethyl)benzene),与过渡金属Zn(II)在水热条件下构筑了配合物1。[Zn_2L~1L~2(mbtz)]·H_2O(1)配合物1中,四个羧基通过双齿配位桥连两个相邻的Zn(II)形成了一个轮浆状的[Zn2(CO2)4]建筑单元,配体L1连接两个相邻的[Zn2(CO2)4]建筑单元构筑了1D链状结构。配体L2连接相邻的1D链形成2D的层状结构,线性含氮配体mbtz把二维层进一步扩展为3D具有6连接的pcu拓扑结构。2、以2,4-二苯甲酰基间苯二甲酸(H_2L~1),2,5-二苯甲酰基对苯二甲酸(H2L2)为主配体,引入新的含氮配体1,3-双(1,2,4-三唑)丙烷为辅助配体,(1,3-bis(1,2,4-triazol-1-yl)propane),通过改变反应条件与过渡金属Zn(II)在水热条件下构筑了配合物2。[Zn_4L_2~1L_2~2(btp)_2]·7H_2O(2)配合物2与1结构非常相似,也是以双核的[Zn2(CO2)4]SBU为6连接点,配体L1,L2,btp为线性连接器构成了三维的pcu拓扑结构。3、以2,5-二苯甲酰基对苯二甲酸(H2L2)为主配体,水热条件下与稀土金属Dy(Ⅲ)构筑了配合物3。[Dy(L2)1.5(H2O)2]·2H2O](3)。在3中,双核[Dy2O4(CO2)6]建筑单元为结点,由L2配体为连接器构筑了三维pcu拓扑结构,拓扑符号为412·63。并对化合物3的热稳定性和荧光性质进行了研究。4、以Wells-Dawson类型的磷钨酸盐为主配体,邻菲罗啉(phen)为辅助配体与过渡金属CuII和在水热条件下合成了化合物4,[Cu(phen)2(H2O)]2+阳离子与[Cu2(phen)3(H2O)3(P2W18O62)]2-阴离子通过π-π作用构筑了1D链,相邻的1D链通过O-H···O分子间作用力拓展为3D超分子结构。此外我们还研究了化合物4的光催化性能。[Cu2(phen)3(H2O)3(P2W18O62)][Cu(phen)2(H2O)]·5H2O(4)。
[Abstract]:The coordination compounds of metal polycarboxylic ligands are novel and unique, and then the potential applications of it are widely used, such as adsorption, magnetism, fluorescence, electrochemistry, catalysis, etc. Besides, the coordination of polycarboxylic ligands is more diverse and more complex than other ligands, and is easy to be assembled. A new unique structure and specific functional coordination compounds. Therefore, the research on the design, synthesis and properties of this kind of complexes has long been concerned by researchers. Polyoxometalate is an excellent inorganic metal oxygen cluster in a comprehensive way. There are many accidents when the complexes are combined with organic ligands to form complexes. In recent years, the design and synthesis of metal organic coordination polymers have been designed and synthesized with the general application of the synthetic methods of polymer (ionic calorimetry, hydrothermal method and solvent heat etc.). By taking Zn (II) as the central ion, 2,4- two benzoyl benzoyl two formic acid and 2,5- two benzoyl terephthalic terephthalic acid as the main ligands, this paper has designed and synthesized 2 unique metal organic coordination polymers in different reaction conditions. The crystal structure analysis, elemental analysis, IR characterization and TGA analysis were carried out and the fluorescence was studied. The results are as follows: 1, 2,4- two benzoyl benzene two formic acid (H_2L~1), 2,5- two benzoyl terephthalic acid (H2L2) as the main ligand, 1,3- double (1,2,4- three azole -1- methyl) benzene as the auxiliary ligand (1,3-bis, 1,3-bis) as the auxiliary ligand (1,3-bis) as the auxiliary ligand (1,3-bis) as the auxiliary ligand (1,3-bis, 1,3-bis) as the auxiliary ligand (1,3-bis). (1,2,4-triazol-1-ylmethyl) benzene), with the transition metal Zn (II) constructed in the hydrothermal condition, the complex 1.[Zn_2L~1L~2 (mbtz)]. H_2O (1) complex 1, the four carboxyl groups formed a pulley like [Zn2 (CO2) 4] building unit through the double tooth distribution bridge and two adjacent Zn (II), and the ligands connected two adjacent building units. 1D chain structure is constructed. Ligand L2 connects adjacent 1D chains to form a layered structure of 2D, and linear nitrogen ligand mbtz extends the two-dimensional layer to 3D with 6 connected PCU topological structure.2, with 2,4- two benzoyl benzoyl benzoic acid (H_2L~1), 2,5- two benzoyl terephthalic terephthalic acid (H2L2) and new nitrogen ligand. Three azole) propane is an auxiliary ligand, (1,3-bis (1,2,4-triazol-1-yl) propane). By altering the reaction conditions and the transition metal Zn (II), the complex 2.[Zn_4L_2~1L_2~2 (BTP) _2]. 7H_2O (2) complex is constructed very similar to the structure of the complex 2 and 1, and the dual nucleus [Zn2 (CO2) 4]SBU is the 6 connection point. A three-dimensional PCU topology.3 is formed, with 2,5- two benzoyl terephthalic acid (H2L2) as the main ligand and 3.[Dy (L2) 1.5 (H2O) 2] 2H2O] (3) complex with rare earth metal Dy (III) under hydrothermal conditions. In 3, the dual core [Dy2O4 (CO2) building unit is a node, and a three-dimensional topological structure is constructed by the ligands, with a topological symbol of 412. 63 The thermal stability and fluorescence properties of compound 3 were studied by.4, with Wells-Dawson type phosphotungstate as the main ligand, adjacent phenanthroline (phen) as the auxiliary ligand and transition metal CuII and synthesis of compound 4, [Cu (phen) 2 (H2O)]2+ cations and [Cu2 (phen) 3 (H2O) 3 (P2W18O62) anion through the pion - pi In the 1D chain, the adjacent 1D chain was extended to 3D supramolecular structure through the intermolecular force of O-H. O. In addition, we also studied the photocatalytic properties of compound 4,.[Cu2 (phen) 3 (H2O) 3 (P2W18O62)][Cu (phen) 2 (H2O)].
【学位授予单位】：长春工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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