张青青, 刘宇奇, 刘强, 王新颖, 李玮, 薛晓斐. 基于含氮杂环配体和二羧酸的过渡金属Zn(Ⅱ)、Co(Ⅱ)配合物的水热合成,晶体结构和性能研究[J]. 云南大学学报(自然科学版), 2020, 42(4): 733-742. doi: 10.7540/j.ynu.20200096
引用本文: 张青青, 刘宇奇, 刘强, 王新颖, 李玮, 薛晓斐. 基于含氮杂环配体和二羧酸的过渡金属Zn(Ⅱ)、Co(Ⅱ)配合物的水热合成,晶体结构和性能研究[J]. 云南大学学报(自然科学版), 2020, 42(4): 733-742. doi: 10.7540/j.ynu.20200096
ZHANG Qing-qing, LIU Yu-qi, LIU Qiang, WANG Xin-ying, LI Wei, XUE Xiao-fei. Hydrothermal synthesis, crystal structure and properties of transition metal zinc and cobalt complexes based on nitrogen-containing heterocyclic ligands and dicarboxylic acids[J]. Journal of Yunnan University: Natural Sciences Edition, 2020, 42(4): 733-742. DOI: 10.7540/j.ynu.20200096
Citation: ZHANG Qing-qing, LIU Yu-qi, LIU Qiang, WANG Xin-ying, LI Wei, XUE Xiao-fei. Hydrothermal synthesis, crystal structure and properties of transition metal zinc and cobalt complexes based on nitrogen-containing heterocyclic ligands and dicarboxylic acids[J]. Journal of Yunnan University: Natural Sciences Edition, 2020, 42(4): 733-742. DOI: 10.7540/j.ynu.20200096

基于含氮杂环配体和二羧酸的过渡金属Zn(Ⅱ)、Co(Ⅱ)配合物的水热合成,晶体结构和性能研究

Hydrothermal synthesis, crystal structure and properties of transition metal zinc and cobalt complexes based on nitrogen-containing heterocyclic ligands and dicarboxylic acids

  • 摘要: 采用水热合成法合成了2种金属有机配合物Zn(tdc)(m-bix)H2O)n (1)和Co5(btx)2(NDC)43-OH)2(H2O)2n (2) (H2tdc=2,5-噻吩二羧酸,m-bix=1,3-二咪唑基亚甲基苯),btx=对二(三氮唑甲基)苯),H2NDC=1,4-萘二甲酸),通过X射线单晶衍射、元素分析、X射线粉末衍射和红外光谱对配合物的结构进行表征.结果表明配合物 1 是四连接的二维层状结构,拓扑符号为44·62,借助于氢键作用力,该配合物拓展成三维超分子网状结构;而配合物 2 则以五核Co53-OH)2(COO)8作为次级结构单元,呈现出拓扑符号为36·434·53·62的罕见的十连接三维结构.此外,光致发光研究表明,配合物 1 在565 nm和605 nm处有发射峰,可作为一种潜在的荧光材料.磁学研究则表明配合物 2 存在弱的反铁磁相互作用,线性拟合得到该配合物的居里外斯温度Tθ=-3.3 K.

     

    Abstract: Two novel metal-organic complexes Zn(tdc)(m-bix)H2O)n (1) and Co5(btx)2(NDC)43-OH)2(H2O)2n (2) (H2tdc=2,5-thiophenedicarboxylic acid, m-bix=1,3-bis (imidazol-1-ylmethyl)-benzene, btx=1,4-bis(1,2,4-triazol-1-ylmethyl) benzene, H2NDC=1,4-naphthalenedicarboxylic acid) have been hydrothermally synthesized. The structure was characterized by techniques of single-crystal X-ray diffraction analysis, elemental analysis, powder X-ray diffraction, infrared spectra, revealing that complex 1 exhibited 4-connected 2D layer structure with the point symbol of 44·62, which extended into 3D supramolecular network by means of hydrogen bonds. While complex 2 featured a rare 3D 10-connected framework with the symbol of 36·434·53·62 based on the pentanuclear Co53-OH)2(COO)8 secondary building unit. In addition, photoluminescence investigations revealed that complex 1 has emission peaks at 565 nm and 605 nm, which can be used as a potential fluorescent material. Furthermore, magnetic analyses indicated that complex 2 showed weakly antiferromagnetic coupling between the Co(II) ions and the magnetic susceptibility datas were rationally fitted with Tθ=−3.3 K.

     

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