双咪唑配位聚合物的合成、结构及荧光性质研究

发布时间：2018-05-12 02:26

  本文选题：配位聚合物 + 咪唑　； 参考：《吉林大学》2016年硕士论文

【摘要】：近几十年来,合理地设计合成结构新颖、性质优异的配位聚合物,吸引了越来越多研究者的目光,成为热点课题之一。众所周知,构建配位化合物主要是通过有机配体和金属离子的配位自组装。因此,有机配体和金属离子的选择,在配合物的合成中显得尤为重要。在众多的有机配体中,通常选择包含羧酸、含氮杂环的有机化合物作为有机连接体。而含有咪唑基的有机化合物作为含氮杂环中的重要组成部分,一直备受研究者的关注。咪唑环中的N原子是很好的π给电子体,易和中心金属离子配位,而且咪唑中的芳环可以产生π-π堆积,这样由含咪唑基配体构筑的配位聚合物通常都具有较好的荧光性质,常被应用于发光材料领域,如:电致发光二极管、荧光探针、爆炸物的检测。同时,d10构型的金属Ag+、Zn2+具有众多的配位模式,可以形成不同的网状结构,并且越来越多的金属银(锌)配位聚合物在室温下展现了优异的荧光性质,是潜在的光学材料。本论文根据晶体工程学原理,选取含有双咪唑基的配体3,5-二咪唑苯腈(DICN)和3,5-二苯并咪唑基苯腈(DBIBN),水热条件下,它们发生原位反应生成配体DIBAH及DBIBAH,配体DIBA-、DICN及DBIBA-和金属银、锌配位得到了10个具有荧光性质的配位聚合物。Ag(DIBA)H2O(1-3),Ag(DICN)Cl O4(4),Ag(DBIBA)(5),Zn(DIBA)(BDC)0.5(6),(H2BDC=对苯二甲酸),Zn(DBIBA)NO3H2O(7),Zn(DBIBA)Cl(8),Zn(DIBA)Cl(9),Zn(DIBA)Cl(H2O)0.5(10)。化合物1-3是具有2D层状结构的配合物,结构中存在着Ag…Ag键和π…π相互作用,分子中的振动导致了1D链间的Ag…Ag键和π…π相互作用发生改变,从而影响了它们的荧光性质,使它们在室温下呈现出不同颜色的荧光。化合物4是由相互垂直的1D链连接成2D的层状结构,并且在室温下有很强蓝绿色的荧光性质,化合物5是具有波浪型2D层状结构的化合物,同时室温下展现出很强的荧光性质。化合物6-10是由金属Zn与含双咪唑基配体构筑的化合物。化合物6是由两个双层相互穿插形成的一个2D层状配合物。它在室温下表现出强的蓝色荧光性质。化合物7-8属于同种构型晶体,均为2D层状结构,由于结构中配位阴离子不同,使它们的荧光性质稍有区别。化合物9-10均是2D层状结构,虽然它们之间的结构稍有不同,但是荧光性质有很大差别,室温下,化合物9表现出黄色荧光,而化合物10却表现出了蓝色荧光,由此可见结构对荧光性质的影响很大。
[Abstract]:In recent decades, the rational design and synthesis of coordination polymers with novel structure and excellent properties have attracted more and more researchers' attention and become one of the hot topics. It is well known that the construction of coordination compounds is mainly through the coordination of organic ligands and metal ions self-assembly. Therefore, the selection of organic ligands and metal ions is particularly important in the synthesis of complexes. Among many organic ligands, organic compounds containing carboxylic acids and nitrogen heterocycles are usually selected as organic connectors. As an important component of nitrogen heterocycles, imidazolyl organic compounds have attracted much attention. The N atom in imidazole ring is a good 蟺 donor, it is easy to coordinate with the central metal ions, and the aromatic ring in imidazole can produce 蟺-蟺 stacking, thus the coordination polymers constructed by imidazolyl ligands usually have better fluorescence properties. Often used in the field of luminescent materials, such as: electroluminescent diodes, fluorescent probes, explosives detection. At the same time, Ag ~ (2 +) Zn _ (2) with d _ (10) configuration has many coordination modes, which can form different network structure, and more Ag (Zn) coordination polymers exhibit excellent fluorescence properties at room temperature and are potential optical materials. According to the principle of crystal engineering, the ligands (DICN) and dibenzimidazolyl benzonitrile (DICN) and dibenzimidazolyl benzonitrile (DBIBN) containing bisimidazolyl group were selected in this paper. Under hydrothermal conditions, the ligands DIBAH and DBIBAH, the ligands DIBA-DICN and DBIBA- and metallic silver were synthesized in situ under hydrothermal conditions, and the ligands DIBA-DICN and DBIBA- and silver were obtained. Ten coordination polymers with fluorescence properties, I. e. Ag-DIBAH _ 2O _ 1-3O _ (+) Ag-DICNN, Cl _ (4) O _ (4) ~ (4) ~ (5) ~ (5) ~ (-) ~ (+) ~ (-) ~ (5) ~ (1) ~ (1) ~ (1) ~ (2) ~ (-) ~ (1) ~ (1) ~ (1) and () ~ (10) ~ (-) ~ (10) ~ (-) ~ (10) for zinc coordination polymer. Compound 1-3 is a complex with 2D layered structure, in which Ag 鈥，

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