高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (11): 2363-2371.doi: 10.7503/cjcu20180347

• 研究论文:无机化学 • 上一篇    下一篇

2-(3'-羧基苯氧基)苯甲酸和含氮配体构筑的过渡金属配合物的合成、 晶体结构及荧光性质

李铮, 李睿, 李夏()   

  1. 首都师范大学化学系, 北京 100048
  • 收稿日期:2018-05-07 出版日期:2018-11-10 发布日期:2018-09-29
  • 作者简介:联系人简介: 李 夏, 女, 博士, 教授, 博士生导师, 主要从事无机配位化学方面的研究. E-mail: xiali@cnu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21471104)和首都师范大学实验室开放基金(批准号: LIP15009S48)资助.

Synthesis, Crystal Structure and Fluorescent Properties of Transition Metal Complexes Constructed with 2-(3'-Carboxyphenoxy)benzoic Acid and N-Donor Ligands

LI Zheng, LI Rui, LI Xia*()   

  1. Department of Chemistry, Capital Normal University, Beijing 100048, China
  • Received:2018-05-07 Online:2018-11-10 Published:2018-09-29
  • Contact: LI Xia E-mail:xiali@cnu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.21471104) and the Open Fund of the Laboratony of Capital Normal University, China(No.LIP15009S48).

摘要:

选用2-(3'-羧基苯氧基)苯甲酸(2,3'-H2oba)、 1,3-双(4-吡啶基)-丙烷(DPP)和1,4-二(1,2,4-三氮唑-1-)丁烷(BTB)为配体, 采用水热法得到了过渡金属配合物Cd(2,3'-oba)(DPP)(1)和Zn(2,3'-oba)(BTB)0.5(2). 配合物1为二维网状结构, 中心Cd2+的配位环境为{CdO4N2}, 双齿螯合配位的2,3'-oba和单齿桥联配位的DPP将Cd2+连接成Cd2+-2,3'-oba-Cd2+-DPP两条螺旋链. 配合物1由分子间氢键连接并自组装为三维超分子结构. 配合物2为三维框架结构, 中心Zn2+采取五配位的畸变四方锥构型{ZnO4N}. 2,3'-oba配体以双齿螯合与双齿桥联的配位方式连接相邻Zn2+并形成二维网层, BTB分子桥联Zn2+并连接相邻网层进而形成三维结构. 荧光光谱表明配合物1和2分别在437和359 nm存在最大发射, 均来源于配体的π* 跃迁. 广谱型农药甲基磺草酮对配合物2的荧光强度具有明显的猝灭作用, 据此配合物2可作为荧光探针检测甲基磺草酮.

关键词: 过渡金属配合物, 2-(3'-羧基苯氧基)苯甲酸, 晶体结构, 荧光性质

Abstract:

Taking 2-(3'-carboxyphenoxy)benzoic acid(2,3'-H2oba), 1,3-bis(4-pyridyl)-propane(DPP) and 1,4-bis(1,2,4-triazole-1-)butane(BTB) as ligands, two transition metal complexes Cd(2,3'-oba)(DPP)(1) and Zn(2,3'-oba)(BTB)0.5(2) were obtained by hydrothermal method. Complex 1 is a two-dimensional network structure, the coordination environment of the central Cd2+ is {CdO4N2}, the 2,3'-oba ligand and the DPP ligand link Cd2+ into Cd2+-2,3'-oba-Cd2+-DPP helical chains by bidentate chelating and monodentate bridging modes, respectively. Complex 1 is linked by intermolecular hydrogen bonding and self-assembled into a three-dimensional supramolecular structure. Complex 2 is a three-dimensional framework structure, and the central Zn2+ adopts a five-coordinated distortion quadrilateral cone configuration {ZnO4N}. The 2,3'-oba ligand links the adjacent Zn2+ as a bidentate chelate and a bidentate bridge to form a two-dimensional network layer. The BTB molecule bridges the Zn2+ and connects adjacent network layers to form a three-dimensional structure. Fluorescence spectroscopy indicates that complexes 1 and 2 have maximum emission at 437 nm and 359 nm, respectively, both are derived from the π*-π transition of the ligand. The broad-spectrum pesticide mesotrione has a significant quenching effect on the fluorescence intensity of complex 2, thus complex 2 can be used as a chemical sensor for detecting mesotrione.

Key words: Transition metal complex, 2-(3'-Carboxyphenoxy)benzoic acid, Crystal structure, Fluorescence

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