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).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-H(3)BTC; 1,4-, 1,2-, and 1,3-H(2)BDC) have yielded a family of inorganic-organic framework materials: [Pb(2)(1,3,5-BTC)(mu(3)-OH)(H(2)O)](n) (Iota), [NaPb(1,3,5-BTC)(H(2)O)](n) (IotaIota), [Pb(1,4-BDC)](n) (IotaIotaIota), [Pb(5)(1,2-BDC)(4)(OAc)(2)](n) (IV), and {[Pb(5)(1,3-BDC)(5)(H(2)O)(2)](2).H(2)O}(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 Pb(4)O(16) 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.

Eight-fold Interpenetrating Diamond-like Metal-Organic Frameworks Constructed with an N- and O-Donor Ligand for Cadmium(II) and Manganese(II)

“…This fluorescence may be tentatively assigned to intra-ligand transitions of the coordinated L − ligands, since a similar emission is observed for the free HL [25,26]. The observed blue shift of the emission maximum for 1 vs. that of HL may be considered to originate from the deprotonation and the metal coordination of the ligand L − [27,28].…”

Zn(II) and Cd(II) Coordination Polymers with an N,O-Donor Ligand: Structural Characterization and Fluorescence Properties

“…As for the origin of fluorescence of the complexes, it may be assigned to intraligand transitions of the coordinated L 2− ligands, since a similar emission can be observed for the free H 2 L ligand [32 -34]. The observed red shifts of the emission maximum for the complexes vs. the H 2 L ligand originate from the coordination interactions [35,36].…”

Two new lead(II) coordination polymer and discrete complex containing bipyridine ligands with different positioned methyl substituents: synthesis, characterization, crystal structure determination, and luminescent properties

“…Melting points were measured on a Kofler Heizbank Rechart type 7841 melting point apparatus and are uncorrected. 1 H and 13 C NMR spectra were recorded on a Bruker 500 DRX Scheme 1 Possible coordination modes of nitrate ligand with Pb(II) Scheme 2 Methyl-substituted 2,2 0 -bipyridine ligands in complexes 1 (5,5 0 -dmbpy) and 2 (6,6 0 -dmbpy) spectrometer, for protons at 500 MHz and for carbons at 125 MHz, in DMSO-d 6 A solution of 6,6 0 -dimethyl-2,2 0 -bipyridine (0.21 g, 1.1 mmol) in CH 3 OH (15 mL) was added to a solution of Pb(NO 3 ) 2 (0.37 g, 1.1 mmol) in CH 3 OH (15 mL) at room temperature and the resulting white precipitant was dissolved in DMSO. The suitable crystals for X-ray diffraction experiment were obtained by methanol diffusion in a solution of white precipitant in DMSO.…”

“…In the past few decades, the potential of coordination polymers as functional materials with useful applications in magnetism, nanomaterial, catalysis, gas adsorption, luminescent, non-linear optical properties, and biological model, as well as for the construction of fascinating architectures with special topology has been very appealing [1][2][3][4][5]. The incorporation of Pb(II) metal ion in the coordination and coordination polymeric systems, in view of their interesting properties and structural features (e.g., adoption of different coordination numbers and the possible occurrence of stereochemical activity for their valence shell lone electron pairs) has been of great interest, in recent years [6][7][8][9][10][11][12].…”