过渡金属配合物中希夫碱和吡啶衍生物混合配体的电子结构、电子能谱分析及吸收光谱分析

IF 2.2 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
Ghouzala Boukehil, Mohamed Amine Zerizer, Sabri Mecheri, Bachir Zouchoune
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引用次数: 0

摘要

利用BP86、PBE和B3LYP泛函对一系列类型为[M(L1)(L2)]2+、[M(L2)2]2+、[M(L2)(L3)2]2+和[M(L3)4]2+的配合物进行了DFT计算(M = Ni、Pd、Cu、Zn, L1 = N-(4甲氧基苄基)异硝基腙双齿希夫碱,L2 = 2,2′-联吡啶,L3 =吡啶)。这类配合物的键合完全合理化,其中预测的结构为M(II)阳离子提供了Ni(II)、Pd(II)和Cu(II)的完美方形平面几何形状,为Zn(II)提供了四面体结构。除了具有双重态自旋的Cu(II)外,所有单重态自旋的优化结构都计算出了较大的HOMO-LUMO间隙;表明了良好的动力学稳定性。Ni(II)、Pd(II)和Zn(II)配合物的低单重态自旋态和Cu(II)配合物的双重态自旋态分别以BP86、PBE和B3LYP官能团为基态,与高三重态和四重态自旋配合物相比。对优化后的几何结构进行了TD-DFT理论研究,使我们能够预测紫外-可见光谱,并根据其分子轨道定位准确地确定光谱位置和不同电子跃迁的性质;因此,可用的实验紫外可见光谱与我们的发现进行了比较。在乙醇溶剂中,由于自由配体与以HOMO→LUMO和HOMO-1→LUMO电子跃迁为特征的金属阳离子的配位,得到了配合物的电子能谱出现了红移。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Electronic structures and EDA-NOCV and absorption spectra analysis of Schiff base and pyridine derivatives mixed ligands in transition metal complexes

DFT calculations using BP86, PBE, and B3LYP functionals have been carried out on a series of complexes of the types [M(L1)(L2)]2+, [M(L2)2]2+, [M(L2)(L3)2]2+, and [M((L3)4]2+ (M = Ni, Pd, Cu, Zn, and L1 = N-(4methoxybenzylidene) isonicotihydrazone bidentate Schiff base, L2 = 2,2′-bipyridine, and L3 = pyridine). A complete rationalization of bonding is provided of these kinds of complexes, where the predicted structures provide to the M(II) cations a perfect square planar geometry for Ni(II), Pd(II), and Cu(II) and a tetrahedral one for Zn(II). Large HOMO–LUMO gaps are calculated for all optimized structures of singlet spin state except for Cu(II) with a doublet spin state; suggesting a good kinetic stability. The low singlet spin state for Ni(II), Pd(II), and Zn(II) and the doublet spin state for Cu(II) complexes are characterized by BP86, PBE, and B3LYP functionals as ground states compared to those of high triplet and quartet spin ones, respectively. The TD-DFT theoretical study performed on the optimized geometries permitted us to predict the UV–Vis spectra and to pinpoint accurately the spectral positions and the nature of the different electronic transitions according to their molecular orbital localization; hence, the available experimental UV–Vis spectra are compared to our findings. The electronic spectra obtained in ethanol solvent show red shifts for complexed species due to the coordination of free ligands with metal cations characterized by HOMO → LUMO and HOMO-1 → LUMO electronic transitions.

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来源期刊
Structural Chemistry
Structural Chemistry 化学-化学综合
CiteScore
3.80
自引率
11.80%
发文量
227
审稿时长
3.7 months
期刊介绍: Structural Chemistry is an international forum for the publication of peer-reviewed original research papers that cover the condensed and gaseous states of matter and involve numerous techniques for the determination of structure and energetics, their results, and the conclusions derived from these studies. The journal overcomes the unnatural separation in the current literature among the areas of structure determination, energetics, and applications, as well as builds a bridge to other chemical disciplines. Ist comprehensive coverage encompasses broad discussion of results, observation of relationships among various properties, and the description and application of structure and energy information in all domains of chemistry. We welcome the broadest range of accounts of research in structural chemistry involving the discussion of methodologies and structures,experimental, theoretical, and computational, and their combinations. We encourage discussions of structural information collected for their chemicaland biological significance.
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