基于烟酸配体的两种新的钛(I)和汞(II)配位聚合物:合成、表征、晶体结构测定和 DFT 计算

IF 2.2 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
Tayyebeh Beyk Mohammadi, Robabeh Alizadeh, Azam Jalalian, Sara Seyfi, Vahid Amani
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引用次数: 0

摘要

通过一个和两个当量的吡啶 3-羧酸(pyc.H)配体分别与 Tl2(CO3) (1) 和 HgBr2 (2) 反应,合成了两个新的配合物 [Tl(pyc)]n (1) 和 {[Hg(pyc.H)(μ-Br)2].C2H5OH}n (2)。这些配合物通过元素分析、紫外光谱、傅立叶变换红外光谱、傅立叶变换核磁共振光谱和发射光谱进行了全面表征,并通过单晶 X 射线衍射法研究了它们的结构。根据 X 射线分析,络合物 1(τ5 = 0.915)在 Tl(I)周围呈现略微扭曲的三叉双锥几何形状,络合物 2(τ5 = 0.062)在 Hg(II)周围呈现略微扭曲的正方形金字塔几何形状。络合物 1 和 2 存在分子间氢键和 π-π 接触(络合物 2),这在稳定晶体结构方面发挥了重要作用。发光研究揭示了游离配体和两种复合物在溶液中的发射特性。此外,本研究还对 Tl(I)配位聚合物 1 进行了密度泛函理论(DFT)分析。单晶 X 射线数据显示,该配合物的优化几何形状非常吻合。分析了包括键长、键角和 HOMO-LUMO 能级在内的分子特性。此外,还使用时间相关密度泛函理论(TD-DFT)方法分析了紫外可见光谱。利用自然键轨道(NBO)分析法研究了复合物 1 中供体-受体相互作用的趋势。此外,部分状态密度(PDOS)计算表明,芳香吡啶配体的 π 特征在价带中起主导作用,而 Tl 轨道的参与可以忽略不计。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Two new coordination polymers of Tl(I) & Hg(II), based on nicotinic acid ligand: synthesis, characterization, crystal structure determination & DFT calculation

Two new coordination polymers of Tl(I) & Hg(II), based on nicotinic acid ligand: synthesis, characterization, crystal structure determination & DFT calculation

Two new coordination polymers of Tl(I) & Hg(II), based on nicotinic acid ligand: synthesis, characterization, crystal structure determination & DFT calculation

Two new complexes, [Tl(pyc)]n (1) and {[Hg(pyc.H)(μ-Br)2].C2H5OH}n (2) have been synthesized by the reaction of one and two equivalent of pyridine 3-carboxylic acid (pyc.H) ligand with Tl2(CO3) (1) and HgBr2 (2), respectively. The complexes were fully characterized by elemental analysis, UV, FT-IR, FT-NMR and emission spectroscopies and their structures were studied by the single-crystal X-ray diffraction method. According to X-ray analysis, complex 1 (τ5 = 0.915) exhibit slightly distorted trigonal bipyramidal geometry around Tl(I) and complex 2 (τ5 = 0.062) shows a slightly distorted square pyramidal geometry around Hg(II). There are intermolecular hydrogen bonding (for complexes 1 and 2) and π-π contacts (for complex 2) which play a significant role in the stabilization of the crystal structure. Luminescence studies revealed the emission properties of free ligand and both complexes in solution. Moreover, in this study, density functional theory (DFT) was performed for Tl(I) coordination polymer 1. The optimized geometry of this complex is shown in good agreement by single crystal X-ray data. Molecular properties including bond lengths, bond angles, and HOMO-LUMO energy levels, were analyzed. Moreover, the UV-Vis spectra were analyzed using time-dependent density functional theory (TD-DFT) method. The tendency of the donor-acceptor interactions in the complex 1 was examined using natural bond orbital (NBO) analysis. In addition, the partial density of states (PDOS) calculation indicates that the π-character of the aromatic pyridine ligand plays role in dominating the valence bands with negligible participation of the Tl orbitals.

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来源期刊
CiteScore
4.40
自引率
8.30%
发文量
230
审稿时长
5.6 months
期刊介绍: JICS is an international journal covering general fields of chemistry. JICS welcomes high quality original papers in English dealing with experimental, theoretical and applied research related to all branches of chemistry. These include the fields of analytical, inorganic, organic and physical chemistry as well as the chemical biology area. Review articles discussing specific areas of chemistry of current chemical or biological importance are also published. JICS ensures visibility of your research results to a worldwide audience in science. You are kindly invited to submit your manuscript to the Editor-in-Chief or Regional Editor. All contributions in the form of original papers or short communications will be peer reviewed and published free of charge after acceptance.
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