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

Abstract

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