基于2,5-二溴对苯二甲酸配体的锌/钴配合物合成、晶体结构及性质

摘要/Abstract

摘要： 将有机物2,5-二溴对苯二甲酸(H₂L₁)和2,2′-联吡啶(L₂)作为双配体,使用溶剂热法和七水合硫酸锌(ZnSO₄·7H₂O)、六水合硝酸钴(Co(NO₃)₂·6H₂O)分别反应,得到配合物[Zn(L₁)(L₂)(H₂O)]_n(1)和配合物[Co(L₁)(L₂)(H₂O)]_n(2)。采用单晶X射线衍射、元素分析、红外光谱、紫外光谱、荧光光谱、热重分析等测试方法对这两种物质进行分析研究。单晶测试结果表明配合物1是单斜晶系,以Zn²⁺配位连接L^2-₁与L₂形成一维链状结构,各条链在分子间氢键和π…π共轭作用下有规律地堆叠形成三维网络结构。配合物2是三斜晶系,Co1离子和Co1ⁱ离子由H₂L₁上的羧酸氧原子O4和O4ⁱ连接,形成双齿螯合的配位结构单元,以Co²⁺配位连接 L^2-₁和L₂形成二维网格结构,各层在O—H…O分子间氢键和范德瓦耳斯力作用下有规律的堆叠形成三维网络结构。配合物1和2均含有芳香杂环、羧基杂环和氮杂环,具有良好的荧光性质和热稳定性,最大发射波长分别为345 nm和333 nm。

关键词: 锌配合物, 钴配合物, 溶剂热法, 2,5-二溴对苯二甲酸, 晶体结构, 荧光性质, 热稳定性

Abstract: In our group, the organic compounds 2,5-dibromoterephthalic acid (H₂L₁) and 2,2′-bipyridine (L₂) were used as biligands to react with zinc sulfate heptahydrate (ZnSO₄·7H₂O) and cobalt nitrate hexahydrate (Co(NO₃)₂·6H₂O), respectively, using solvothermal method to obtain a zinc complex [Zn(L₁)(L₂)(H₂O)]_n (1) and a cobalt complex [Co(L₁)(L₂)(H₂O)]_n (2). The structural characterization and properties measurement were performed by single crystal X-ray diffraction, elemental analysis, infrared spectroscopy, ultraviolet spectroscopy, fluorescence spectroscopy, thermogravimetric analysis and other tests. The results show that complex 1 is a monoclinic crystal system with one-dimensional chain structure formed by the coordination of Zn²⁺ linking L^2-₁ and L₂, each chain forming a three-dimensional network structure by regular stacking under intermolecular hydrogen bonding and π…π conjugation. Complex 2 is a triclinic crystal system with Co1 and Co1ⁱ ions linked by carboxylic acid oxygen atoms O4 and O4ⁱ on H₂L₁ to form a bidentate chelated ligand structural unit. A two-dimensional lattice structure is formed with Co²⁺ ligands connecting L^2-₁ and L₂, and the layers are regularly stacked under O—H…O intermolecular hydrogen bonding and van der Waals forces to form a three-dimensional network structure. Both complexes 1 and 2 contain aromatic heterocycles, carboxyl heterocycles and nitrogen heterocycles, they have good fluorescence property and thermal stability, the maximum emission wavelengths of complex 1 and complex 2 are 345 nm and 333 nm, respectively.

Key words: zinc complex, cobalt complex, solvothermal method, 2, 5-dibromoterephthalic acid, crystal structure, fluorescence property, thermal stability

中图分类号:

O641

黄瑞琴, 王胜, 刘峥, 唐群, 魏润芝. 基于2,5-二溴对苯二甲酸配体的锌/钴配合物合成、晶体结构及性质[J]. 人工晶体学报, 2022, 51(11): 1944-1951.

HUANG Ruiqin, WANG Sheng, LIU Zheng, TANG Qun, WEI Runzhi. Synthesis, Crystal Structure and Properties of Zn/Co Complexes Based on 2, 5-Dibromoterephthalic Acid Ligands[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(11): 1944-1951.

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