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3,4'-联苯二甲酸与含氮配体构筑的镧系配合物的合成、晶体结构及荧光传感
Syntheses, Crystal Structures and Fluorescence Sensing of Lanthanide Complexes with 3,4'-Biphenyldicarboxylic Acid and N-donor Ligands
作者单位E-mail
周鑫 首都师范大学化学系, 北京 100048  
张美娜 首都师范大学化学系, 北京 100048  
张德春 首都师范大学化学系, 北京 100048  
李夏 首都师范大学化学系, 北京 100048 xiali@mail.cnu.edu.cn 
姚颖芳 首都师范大学化学系, 北京 100048  
摘要: 通过水热方法合成了2个镧系配合物,[Gd(3,4'-dpdc)2(HDPP)]n1)和{[Dy(3,4'-Hdpdc)3(H2O)]·0.5BTB}n2)(3,4'-H2dpdc=3,4'-联苯二甲酸,DPP=1,3-二(4-吡啶基)-丙烷,BTB=1,4-二(1,2,4-三氮唑)-1-丁烷),通过X射线单晶衍射对其结构进行表征。配合物1属单斜晶系,P21/c空间群。该配合物为二维层状结构,中心Gd(Ⅲ)离子的配位环境为[GdO7N]。3,4'-dpdc配体以μ1η1η1/μ2η1η1μ1η1η1/μ1η1η0两种方式桥联Gd(Ⅲ)离子,而HDPP配体是以端基的形式配位于Gd(Ⅲ)离子。配合物2属三斜晶系,P1空间群。配合物2具有一维链状结构,Dy(Ⅲ)离子的配位环境为[DyO7]。3,4'-Hdpdc配体以μ2η1η1配位模式链接相邻的Dy(Ⅲ)离子。未参加配位的BTB通过氢键与一维链连接,进而形成三维超分子结构。固态光致发光测量表明,化合物12在350~650 nm范围内显示出宽峰,归因于配体的π*π跃迁。进一步研究了水溶液中不同沙星类药物对配合物1的发光的影响,实验结果表明该配合物可以识别培氟沙星。
关键词: 镧系配合物  3,4'-联苯二甲酸  晶体结构  荧光
基金项目: 国家自然科学基金(No.21471104)资助项目。
Abstract: Two lanthanide complexes,[Gd(3,4'-dpdc)2(HDPP)]n (1) and {[Dy(3,4'-Hdpdc)3(H2O)]·0.5BTB}n (2) (3,4'-H2dpdc=3,4'-biphenyldicarboxylic acid, DPP=1,3-bis(4-pyridyl)propane, BTB=1,4-bis(1,2,4-triazol-1-yl)butane) were successfully synthesized under hydrothermal reactions, and their structures were characterized by single crystal X-ray diffraction. Complex 1 belongs to monoclinic system, space group P21/c. It is two-dimensional layered structure and consists of[GdO7N] unit. 3,4'-dpdc ligands are connected to the Gd(Ⅲ) ions by μ1:η1η1/μ2:η1η1 and μ1:η1η1/μ1:η1η0 coordination modes. DPP ligands are end-coordinated to Gd(Ⅲ) ions. Complex 2 is a triclinic system, space group P1. The complex shows a one-dimensional chain structure. The coordination environment of Dy(Ⅲ) ion is[DyO7]. The 3,4'-Hdpdc ligands link Dy(Ⅲ) ions in a μ2:η1η1 coordination mode. The BTB molecules are connected to the one-dimensional chains by hydrogen bonds and thus form a three-dimensional supramolecular structure. Solid state photoluminescence measurements show that compounds 1 and 2 display broad band in the range of 350~650 nm due to the π*π transition of the ligands. The effect of different floxacins on the luminescence of complex 1 in aqueous solution was studied. The results showed that the complex could identify pefloxacin.
Keywords: lanthanide complex  3,4'-biphenyldicarboxylic acid  crystal structure  fluorescence
投稿时间:2018-01-25 修订日期:2018-04-02
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周鑫,张美娜,张德春,李夏,姚颖芳.3,4'-联苯二甲酸与含氮配体构筑的镧系配合物的合成、晶体结构及荧光传感[J].无机化学学报,2018,34(7):1285-1292.
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