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由于在气体存储、分离、药物传输、催化、导电、手性、荧光、磁性和非线性光学等领域有广阔的应用前景,具有新颖结构和特殊物化性质的配位聚合物的研究引起人们极大兴趣.通常,选择含适当功能基团的配体是构筑功能配位聚合物关键.其中,含氮五元杂环(如咪唑、三唑和四唑)及其衍生物类配体被人们广泛研究,本课题组也在此领域开展了一些工作.我们以苯并咪唑和1,4-二溴苯合成了配体1,4-双(苯并咪唑)苯,并以此为桥连配体来构筑具有特殊功能的配位聚合物.选择此配体主要基于以下几点:(1)配体呈中性,可以通过选择含不同抗衡阴离子的金属盐来实现对配合物的结构调控作用;(2)配体为刚性,而且配位模式单一,从而减小了配体本身对配合物结构的影响;(3)配体含大芳香环,因此能具有好的发光性质.在本文中,我们以1,4-双(苯并咪唑)苯和相应的金属盐合成了三个配位聚合物{[Co(L)(SO4)(H2O)](CH3OH)}∞(1),{[Cd(L)2(SiF6)](H2O)}∞(2)和[Zn(L)(NO3)2]∞(3).通过红外、元素分析和单晶X光衍射表征了化合物的结构.在配合物1中,硫酸根把钴离子连接成一维链,再通过1,4-双(苯并咪唑)苯连接成三维金刚石网络;而配合物2中,六氟硅酸根把镉离子连接成一维链,再通过1,4-双(苯并咪唑)苯连接成三维α-Po网络,而且化合物沿c轴方向存在一维孔道;3则具有一维Z字链结构,并通过π-π相互作用构筑成二维超分子网络.比较了具有不同配位能力的阴离子对化合物结构的影响.配合物1的磁性研究表明金属钴中心之间都存在明显的反铁磁性相互作用.研究了配合物2和3室温时固态荧光性质.配合物2在361nm出现强的荧光发射,对应于配体的π→π*和n→π*能级跃迁;配合物3在414nm出现紫色荧光,表明化合物存在明显的能量转移.
Due to its broad applications in gas storage, separation, drug delivery, catalysis, conductivity, chirality, fluorescence, magnetism and nonlinear optics, the study of coordination polymers with novel structure and special physico-chemical properties has attracted great attention Interests Generally, the selection of ligands with appropriate functional groups is the key to building functional coordination polymers, among which nitrogen-containing five-membered heterocyclic rings (such as imidazole, triazole and tetrazole) and their derivatives are widely used Research, our group has also carried out some work in this area.We synthesized the ligand 1,4-bis (benzimidazole) benzene with benzimidazole and 1,4-dibromobenzene as a bridging To construct a coordination polymer with special functions.The ligand is selected based on the following points: (1) The ligand is neutral, and the structure regulation of the complex can be achieved by selecting the metal salts with different counterions ; (2) The ligand is rigid and the coordination mode is single, thus reducing the ligand’s own influence on the structure of the complex; (3) The ligand contains a large aromatic ring and therefore has good luminescent properties. , We synthesized 1,4-bis (benzimidazole) benzene and the corresponding metal salts (1), {[Cd (L) 2 (SiF6)] (H2O)} ∞ (2) and [Zn The structure of the compound was characterized by IR, elemental analysis and single crystal X-ray diffraction. In the complex 1, the sulfate ion links the cobalt ion into one-dimensional chain, (2-benzimidazole) benzene links into a three-dimensional diamond network. In complex 2, hexafluorosilicate connects cadmium ions into a one-dimensional chain, which is then connected to a 3- Po network, and there is a one-dimensional pore along the c-axis in the compound, and a one-dimensional Z-chain structure in the third and a two-dimensional supramolecular network through π-π interaction.Compared to the compound with different coordination ability Structure of complex 1. The magnetic studies of complex 1 show that there are obvious antiferromagnetic interactions among the metal cobalt centers.The solid state fluorescence properties at room temperature of complexes 2 and 3 were studied.The strong fluorescence emission of complex 2 at 361 nm, Corresponding to the π → π * and n → π * transitions of the ligands; complex 3 shows purple fluorescence at 414 nm, indicating that there is a significant energy transfer of the compound.