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

通过水热方法合成了2个镧系配合物,[Gd(3,4′-dpdc)_2(HDPP)]_n(1)和{[Dy(3,4′-Hdpdc)_3(H_2O)]·0.5BTB}_n(2)(3,4′-H_2dpdc=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,P2_1/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[GdO_7N]。3,4′-dpdc配体以μ_1∶η~1η~1/μ_2∶η~1η~1和μ_1∶η~1η~1/μ_1∶η~1η~0两种方式桥联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[Dy O7]。3,4′-Hdpdc配体以μ_2∶η~1η~1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1和2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。

Two lanthanide complexes, [Gd（3,4′-dpdc）2（HDPP）]n（1） and {[Dy（3,4′-Hdpdc）3（H2O）]·0.5 BTB}n（2）（3,4′-H2 dpdc=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∶η~1η~1/μ2∶η~1η~1 and μ1∶η~1η~1/μ1∶η~1η~0 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∶η~1η~1 coordination mode. The BTB molecules are connected to the one-dimensional chains by hydrogen bonds and thus form a threedimensional 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. CCDC：1814250, 1; 1814251, 2.