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

Synthesis, Crystal Structure and Properties of Zn/Co Complexes Based on 2, 5-Dibromoterephthalic Acid Ligands

将有机物2,5-二溴对苯二甲酸(H_(2) L_(1))和2,2′-联吡啶(L_(2))作为双配体,使用溶剂热法和七水合硫酸锌(ZnSO_(4)·7H_(2) O)、六水合硝酸钴(Co(NO_(3))_(2)·6H_(2) O)分别反应,得到配合物[Zn(L_(1))(L_(2))(H_(2) O)]_(n)(1)和配合物[Co(L_(1))(L_(2))(H_(2) O)]_(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Zn^(2+)配位连接L_(2)-1与L_(2)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H_(2) L_(1)上的羧酸氧原子O_(4)和O_(4)^(i)连接,形成双齿螯合的配位结构单元,以Co^(2+)配位连接L_(2)-1和L_(2)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。

In our group,the organic compounds 2,5-dibromoterephthalic acid(H_(2) L_(1))and 2,2′-bipyridine(L_(2))were used as biligands to react with zinc sulfate heptahydrate(ZnSO_(4)·7H_(2) O)and cobalt nitrate hexahydrate(Co(NO_(3))_(2)·6H_(2) O),respectively,using solvothermal method to obtain a zinc complex[Zn(L_(1))(L_(2))(H_(2) O)]_(n)(1)and a cobalt complex[Co(L_(1))(L_(2))(H_(2) O)]_(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 Zn^(2+)linking L_(2)-1 and L_(2),each chain forming a three-dimensional network structure by regular stacking under intermolecular hydrogen bonding andπ…πconjugation.Complex 2 is a triclinic crystal system with Co1 and Co1i ions linked by carboxylic acid oxygen atoms O_(4) and O_(4)^(i) on H_(2) L_(1) to form a bidentate chelated ligand structural unit.A two-dimensional lattice structure is formed with Co^(2+)ligands connecting L_(2)-1 and L_(2),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.