基于柔性配体的双核铽配位聚合物[Tb2(tda)3(H2O)2]的合成、晶体结构和荧光性质

在水热条件下，利用硫代羟基二乙酸配体[thiodiglycolic acid=H₂tda]和TbCl₃·nH₂O合成了新型稀土配合物[Tb₂(tda)₃(H₂O)₂]。单晶结构表明，配合物是以共边多面体[Tb₂O₁₆]为基本单元构筑的二维结构，并通过弱相互作用拓展为三维超分子体系。中心原子铽与氧原子的配位数是8和9，分别形成了单帽反四棱柱和三帽三角棱柱构型的空间配位多面体。配体H₂tda在配合物中存在两种配位模式：(a) 双“顺-顺桥式双齿、螯合桥式三齿”模式和(b) 双“螯合双齿、顺-反桥式双齿”模式。荧光光谱研究表明：该配合物在室温下呈现较强的绿色荧光发射。配合物属三斜晶系，空间群P1。

Dinuclear Terbium Coordination Polymer Based on Flexible Ligand: Synthesis, Crystal Structures and Luminescence Properties of [Tb2(tda)3(H2O)2]

The lanthanide coordination polymer, Tb2(tda)3(H2O)2, and it's single crystals was self-assembled from thiodiglycolic acid (H2tda) and corresponding terbium (Ⅲ) chlorides under hydrothermal conditions. Single-crystal structure shows that the compound presents a 2D network, an edge-sharing dinuclear polyhedral [Tb2O16] was found to be the building unit of the network, in which the eight-coordinated TbO8and nine-coordinated TbO9 cores exhibit distinct coordination environments, that is, one is in a distorted monocapped square antiprism surrounding and the other is in a triply capped trigonal prism. The H2tda ligand exhibits two different coordination modes in framework, including mode a: Bis "syn, syn-bridging bidentate, chelating-bridging tridentate", mode b: Bis "chelating-bridging bidentate, syn, anti-bridging bidentate". Eventually, through the weak interaction, the networks formed 3D supramolecular architectures. Photoluminescence measurements indicate that the terbium compound is a strong green emitter in the solid state at room temperature. Crystal data for the complex: triclinic. Space group P(1), with a=0.79466(8)nm, b=1.06796(11)nm, c=1.43323(14)nm,α=70.51700(10)°,β=75.6480(2)°,γ=76.9750(2)°, V=109726(19)nm3, and Z=2. CCDC:667667.