A new coordination polymer of Cd(II) with 4-methyl-1,2,4-triazole-3-thiol ligand: synthesis, characterization, crystal structure, photoluminescence and DFT calculation
Nastaran Pour Ghasem, Robabeh Alizadeh, Sara Seyfi, Vahid Amani
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引用次数: 0
Abstract
A new Cadmiun(II) coordination polymer, {[Cd(µ-mptrz)2].0.5((CH3)2SO)}n was prepared from the reaction of CdBr2 with 4-methyl-4H-1,2,4-triazole-3-thiol (Hmptrz) ligand in methanol. The coordination polymer was thoroughly characterized by elemental analysis, IR, UV–Vis, 1HNMR spectroscopies, and thermogravimetric analysis. Moreover, its structure was studied by the single-crystal diffraction method. Compound 1 has a 1D chain structure. Furthermore, crystal structure is stabilized by intermolecular weak interactions, for example, C–H···O, C–H···N, and C–H···S hydrogen bonds. Besides, the photoluminescence of 1 has been investigated. This compound exhibits photoluminescence with an emission maximum of 321 nm upon excitation at 259 nm. The present work is a combined experimental and computational study. Quantum chemical parameters such as bond lengths, bond angles, HOMO–LUMO energy levels, energy band gap \(\Delta E\), chemical hardness η, the dipole moment μ, and Natural bond orbital (NBO) analysis of the compound were investigated using the DFT at M06/GENECP (6-31 g(d) and LANL2DZ) basis sets for compound 1. Our calculation results have shown that compound 1 has an energy band gap (∆E = 3.857 eV), indicating a high recommendation for a semiconductor compound. The optimized geometry of the Cd(II) coordination polymer is shown in good agreement with single crystal X-ray data. UV/Vis spectra are calculated with the time-dependent density functional theory (TD-DFT) method. Furthermore, TD-DFT displays intraligand transition (ILCT) between triazole bridging ligands. Moreover, NBO analysis of the Cd(II) coordination polymer indicates that the lone pair donor orbital interaction between the N, S, and O lone pairs and π*, σ* anti-bonding orbitals provides stronger stability. Additionally, Solid-state density functional theory (DFT) calculations were performed on 1 using the program VASP to understand the electronic states and conduction pathways of the coordination polymer.
期刊介绍:
Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance.
Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.