Synthesis, Structure, and Luminescent Properties of Hybrid Inorganic−Organic Framework Materials Formed by Lead Aromatic Carboxylates: Inorganic Connectivity Variation from 0D to 3D

The hydro(solvo)thermal reactions of Pb(OAc)2·3H2O with the aromatic carboxylic ligands 1,3,5-benzenetricarboxylic and 1,4-, 1,2-, and 1,3-benzenedicarboxylic acids (1,3,5-H3BTC; 1,4-, 1,2-, and 1,3-H2BDC) have yielded a family of inorganic−organic framework materials: [Pb2(1,3,5-BTC)(μ3-OH)(H2O)]n (Ι), [NaPb(1,3,5-BTC)(H2O)]n (ΙΙ), [Pb(1,4-BDC)]n (ΙΙΙ), [Pb5(1,2-BDC)4(OAc)2]n (IV), and {[Pb5(1,3-BDC)5(H2O)2]2·H2O}n (V). These complexes have been characterized by means of single-crystal X-ray diffraction, X-ray powder diffraction, thermogravimetric analysis−mass spectrometry, and photoluminescence spectra. They are all three-dimensional structures except for two-dimensional IV. Topology analysis reveals that complexes I an V represent rare (4,8)-connected flu and (3,4)-connected zeolite-like nets, respectively. The five complexes exhibit diverse inorganic connectivity, including a 0D Pb4O16 cluster for I, a 1D Pb−O−Pb chain for II, a 2D Pb−O−Pb network for III and IV, and an unprecedented 3D Pb−O−Pb framework for V. And the diversity in inorganic arrays leads to differences in luminescent properties of these complexes.

将三水合乙酸铅（Pb(OAc)₂·3H₂O）与芳香羧酸配体1,3,5-苯三甲酸（1,3,5-H₃BTC）、1,4-、1,2-及1,3-苯二甲酸（1,4-,1,2-,1,3-H₂BDC）进行水（溶剂）热反应，得到了一系列无机-有机骨架材料：[{Pb₂(1,3,5-BTC)(μ₃-OH)(H₂O)}]ₙ（Ι）、[NaPb(1,3,5-BTC)(H₂O)]ₙ（ΙΙ）、[Pb(1,4-BDC)]ₙ（ΙΙΙ）、[{Pb₅(1,2-BDC)₄(OAc)₂}]ₙ（IV）以及{[Pb₅(1,3-BDC)₅(H₂O)₂]₂·H₂O}ₙ（V）。上述配合物均通过单晶X射线衍射、X射线粉末衍射、热重-质谱联用分析以及光致发光光谱进行了表征。除二维结构的配合物IV外，其余配合物均为三维骨架结构。拓扑分析结果表明，配合物Ι与V分别属于罕见的(4,8)连接flu拓扑与(3,4)连接的类沸石骨架网。五种配合物展现出多样化的无机连接模式：配合物Ι为0维Pb₄O₁₆簇，配合物ΙΙ为一维Pb-O-Pb链，配合物ΙΙΙ与IV为二维Pb-O-Pb网络，而配合物V则拥有前所未有的三维Pb-O-Pb骨架。无机骨架阵列的差异最终导致了各配合物发光性能的差异。