高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (2): 253-261.doi: 10.7503/cjcu20190493

• 研究论文:无机化学 • 上一篇    下一篇

4-(4-羧基苯氧基)间苯二甲酸构筑的过渡金属配位聚合物: 合成、 晶体结构、 荧光传感与光催化

刘东枚,苏雅静,李姗姗,许奇炜,李夏()   

  1. 首都师范大学化学系, 北京 100048
  • 收稿日期:2019-09-16 出版日期:2020-02-10 发布日期:2019-10-29
  • 通讯作者: 李夏 E-mail:xiali@cnu.edu.cn
  • 基金资助:
    国家自然科学基金(21471104);首都师范大学实验室开放基金资助(LIP18009S047)

Transition Metal Coordination Polymers Constructed by 4-(4-Carboxyphenoxy)isophthalic Acid: Synthesis, Crystal Structure, Fluorescence Sensing and Photocatalysis

LIU Dongmei,SU Yajing,LI Shanshan,XU Qiwei,LI Xia()   

  1. Department of Chemistry, Capital Normal University, Beijing 100048, China
  • Received:2019-09-16 Online:2020-02-10 Published:2019-10-29
  • Contact: Xia LI E-mail:xiali@cnu.edu.cn
  • Supported by:
    ? Supported by the National Natural Science Foundation of China(21471104);the Laboratory Opening Fund of Capital Normal University, China(LIP18009S047)

摘要:

采用水热法合成了4个配位聚合物[Zn(Hcpoia)(2,2'-bpy)·H2O]n(1)和[M(Hcpoia)(phen)]n·nH2O[M=Zn(2), Mn(3), Co(4); H3cpoia=4-(4-羧基苯氧基)间苯二甲酸; 2,2'-bpy=2,2'-联吡啶; phen=1,10-邻菲罗啉], 利用X射线单晶衍射分析确定了配合物的晶体结构. 配合物1为一维链状结构, 中心Zn 2+离子的配位环境为[ZnO4N2]扭曲的八面体构型, 配体Hcpoia 2-μ1η 1η 0μ1η 1η 1配位模式桥连相邻的Zn 2+离子. 配合物2和4的结构与配合物1类似, 是由配体Hcpoia 2-μ1η 1η 0μ1η 1η 1配位模式联接[MO4N2]结构单元而形成的一维链状结构. 配合物1, 2和4中均存在分子间氢键(O—H…O), 氢键的存在使一维链连接形成二维超分子结构. 配合物3为二维网状结构, Mn 2+离子的配位环境为[MnO4N2]扭曲的八面体构型, 配体Hcpoia 2-μ2η 1η 1配位模式桥连相邻Mn 2+离子形成[Mn2COO2]结构单元, 该结构单元被Hcpoia 2-连接形成二维结构. 在4个配合物中, 2,2'-bpy和phen配体均以端基的形式与金属离子螯合配位. 研究了水溶液中抗生素分子和Fe 3+离子对配合物1与荧光强度的影响, 实验结果表明, 甲硝唑、 Fe 3+离子对配合物1有荧光猝灭作用, 并进一步考察了甲硝唑浓度和Fe 3+离子浓度对配合物1荧光强度的影响. 基于荧光猝灭机理, 配合物1可以用作荧光传感器检测水溶液中的甲硝唑和Fe 3+离子. 研究了配合物4对罗丹明B(RhB)的催化降解性能, 发现在氙灯照射和H2O2存在条件下, 配合物4对RhB具有较好的光催化降解作用.

关键词: 过渡金属配位聚合物, 晶体结构, 荧光, 光催化

Abstract:

Four new transition metal coordination polymers, [Zn(Hcpoia)(2,2'-bpy)·H2O]n(1) and [M(Hcpoia)(phen)]n·nH2O[M=Zn(2), Mn(3), Co(4); H3cpoia=4-(4-carboxyphenoxy)isophthalic acid; 2,2'-bpy=2,2'-bipyridine; phen=1,10-phenanthroline], were synthesized by hydrothermal method and characterized by X-ray single crystal diffraction(XRD). Complex 1 features a one-dimensional chain structure, and Zn 2+ ions adopt a [ZnO4N2] distorted octahedral configuration. Zn 2+ ions are linked by Hcpoia 2- ligands through μ1η 1η 0 and μ1η 1η 1 coordination modes. The structures of complexes 2 and 4 are similar to that of complex 1 with one-dimensional chain structure, which is formed by Hcpoia 2- ligands connecting [MO4N2] structural units through μ1η 1η 0/μ1η 1η 1 coordination modes. The one-dimensional chains of complexes 1, 2 and 4 are developed into two-dimensional structures by intermolecular hydrogen bonds. Complex 3 has a two-dimensional network structure, in which Mn 2+ ions take a [MnO4N2] distorted octahedral configuration. Hcpoia 2- ligands link adjacent Mn 2+ ions through μ1η 1η 0 and μ1η 1η 1 coordination modes to form [Mn2COO2] binuclear units. The binuclear units are connected by Hcpoia 2- ligands to form a two-dimensional structure. In complexes 1—4, both 2,2'-bpy and phen ligands as terminal groups chelate to metal ions. The effects of antibiotics and Fe 3+ ions in aqueous solution on the fluorescence intensity of complex 1 were studied. The results show that metronidazole and Fe 3+ ions exert quenching effects on fluorescence of complex 1. The effects of various concentrations of metronidazole and Fe 3+ ions on the fluorescence intensity of complex 1 were further studied. Based on the fluorescence quenching mechanism, complex 1 can be used as a fluorescence sensor for detection of metronidazole and Fe 3+ ions in aqueous solution. The catalytic performance of complex 4 on RhB was studied. The experimental results show that complex 4 has good photocatalytic degradation of RhB in the presence of hydrogen peroxide and xenon lamp irradiation.

Key words: Transition metal coordination polymer, Crystal Structure, Fluorescence, Photocatalysis

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