Nickel(II) complexes of 2-hydroxy-benzaldehyde-thiosemicarbazone: Catalase inhibition, antioxidant, DFT, and chemical activities

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron Pub Date : 2025-09-15 DOI:10.1016/j.poly.2025.117789

Şükriye Güveli , Namık Özdemir , Mustafa Özyürek , Tülay Bal-Demirci , Bahri Ülküseven

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Abstract

The mixed ligand nickel(II) complexes with an ONS coordination mode were synthesized by reacting N-methyl- and N-phenyl-thiosemicarbazone ligands derived from 3-bromo-5-chloro-2-hydroxy-benzaldehyde with triphenylphosphine and characterized. In the molecular structure of the complexes (1 and 2), the nickel center has a distorted square planar environment via ONSP atoms. The antioxidant capacities by CUPRAC, free radical scavenging activities by DPPH, and the catalase enzyme (CAT) inhibitory activities of the synthesized compounds with ONS coordination mode and previously prepared complexes with ONN mode were investigated. The CUPRAC studies showed that the ligands and their complexes containing ONS donors provide much more activity than those having ONN donors. According to the results, 1 was found to have the most effective CAT activity. Furthermore, Density Functional Theory (DFT) studies were conducted at the CAM-B3LYP/cc-pVDZ/LANL2DZ(Ni) level to gain deeper insights into the structural, chemical, spectroscopic, and electronic properties of the compounds. In general, there was an acceptable agreement between the experimental and theoretical structural and spectroscopic results. The energy gap between the highest occupied molecular orbitals (HOMO) and lowest unoccopied (LUMO) was found 6.119 and 6.007 eV for 1 and 2, respectively. Computational studies have compared the differences in chemical activity between the ONS and ONN systems and supported the higher activity of ONS complexes.

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2-羟基-苯甲醛-硫代氨基脲镍（II）配合物：过氧化氢酶抑制、抗氧化、DFT和化学活性

以3-溴-5-氯-2-羟基苯甲醛为配体，n -甲基和n -苯基硫代氨基脲为配体，与三苯基膦反应，合成了具有ONS配位模式的混合配体镍（II）配合物，并进行了表征。在配合物（1和2）的分子结构中，镍中心通过ONSP原子具有扭曲的方形平面环境。考察了CUPRAC的抗氧化能力、DPPH的自由基清除能力以及ONS配合物和ONN配合物对过氧化氢酶（CAT）的抑制活性。CUPRAC的研究表明，含有ONN供体的配体及其复合物比含有ONN供体的配体提供更多的活性。根据结果，发现1具有最有效的CAT活性。此外，在CAM-B3LYP/cc-pVDZ/LANL2DZ（Ni）水平上进行了密度泛函理论（DFT）研究，以更深入地了解化合物的结构、化学、光谱和电子性质。总的来说，实验和理论的结构和光谱结果是一致的。1和2的最高已占据分子轨道（HOMO）和最低未复制分子轨道（LUMO）之间的能隙分别为6.119和6.007 eV。计算研究已经比较了ONS和ONN体系之间化学活性的差异，并支持了ONS复合物的更高活性。

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.