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)center dot 3H(2)O 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: [Pb-2(1,3,5-BTC)(mu(3)-OH)(H2O)](n) (I), [NaPb(1,3,5-BTC)(H2O)](n) (II), [Pb(1,4-BDC)](n) (III), [Pb-5(1,2-BDC)(4)(OAc)(2)](n) (IV), and {[Pb-5(1,3-BDC)(5)(H2O)(2)](2)center dot 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 1, 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.