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

IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
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.

Abstract Image

Abstract Image

镉(II)与 4-甲基-1,2,4-三唑-3-硫醇配体的新型配位聚合物:合成、表征、晶体结构、光致发光和 DFT 计算
由 CdBr2 与 4-甲基-4H-1,2,4-三唑-3-硫醇(Hmptrz)配体在甲醇中反应制备了一种新的镉锰(II)配位聚合物 {[Cd(µ-mptrz)2].0.5((CH3)2SO)}n。通过元素分析、红外光谱、紫外可见光谱、1HNMR 光谱和热重分析对配位聚合物进行了全面的表征。此外,还利用单晶衍射法研究了其结构。化合物 1 具有一维链状结构。此外,晶体结构还受到分子间弱相互作用的稳定,例如 C-H--O、C-H--N 和 C-H-S 氢键。此外,还对 1 的光致发光进行了研究。该化合物在 259 纳米波长的激发下发出 321 纳米波长的最大光致发光。本研究是一项实验与计算相结合的研究。使用 M06/GENECP (6-31 g(d) 和 LANL2DZ) 基集的 DFT 对化合物 1 的键长、键角、HOMO-LUMO 能级、能带间隙、化学硬度 η、偶极矩 μ 等量子化学参数以及自然键轨道 (NBO) 分析进行了研究。计算结果表明,化合物 1 具有能带隙 (∆E = 3.857 eV),这表明该化合物具有较高的半导体化合物推荐性。镉(II)配位聚合物的优化几何形状与单晶 X 射线数据十分吻合。紫外/可见光谱是用时变密度泛函理论(TD-DFT)方法计算得出的。此外,TD-DFT 还显示了三唑桥配体之间的配体内转变(ILCT)。此外,对 Cd(II) 配位聚合物的 NBO 分析表明,N、S 和 O 孤对供体轨道与 π*、σ* 反键轨道之间的相互作用提供了更强的稳定性。此外,还使用 VASP 程序对 1 进行了固态密度泛函理论(DFT)计算,以了解配位聚合物的电子状态和传导途径。
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来源期刊
Accounts of Chemical Research
Accounts of Chemical Research 化学-化学综合
CiteScore
31.40
自引率
1.10%
发文量
312
审稿时长
2 months
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.
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