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  

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

作　　者：刘东枚 苏雅静 李姗姗 许奇炜 李夏[1] LIU Dongmei;SU Yajing;LI Shanshan;XU Qiwei;LI Xia(Department of Chemistry,Capital Normal University,Beijing 100048,China)

机构地区：[1]首都师范大学化学系

出　　处：《高等学校化学学报》2020年第2期253-261,共9页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21471104);首都师范大学实验室开放基金(批准号:LIP18009S047)资助~~

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-以μ1∶η1η0和μ1∶η1η1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-以μ1∶η1η0和μ1∶η1η1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-以μ2∶η1η1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。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 μ1∶ η^1η^0 and μ1∶ η^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 μ1∶ η^1η^0/μ1∶ η^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 μ1∶ η^1η^0 and μ1∶ η^1η^1 coordination modes to form [Mn2COO2]binuclear units. The binuclear units are connected by Hcpoia2-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 complex1 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 i

关 键 词：过渡金属配位聚合物 晶体结构 荧光 光催化 

分 类 号：O614[理学—无机化学]