具有低对称性四价配体的八面体镍(II)配合物的结构与零场分裂之间的关系

IF 4.6 Q2 MATERIALS SCIENCE, BIOMATERIALS
H. Sakiyama, Rin Kimura, Haruto Oomiya, R. Mitsuhashi, Sho Fujii, K. Kanaizuka, M. Muddassir, Yuga Tamaki, E. Asato, Makoto Handa
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引用次数: 0

摘要

八面体镍(II)配合物是最简单的体系之一,它们通过拥有两个未成对电子而表现出零场分裂。为了阐明低对称体系中结构与零场分裂之间的关系,研究人员用四价配体 2-[双(2-甲氧基乙基)氨基甲基]-4-硝基苯酚(1-)[(onp)-]制备了变形八面体镍(II)配合物。复合物[Ni(onp)(dmso)(H2O)][BPh4]-2dmso (1)(dmso = 二甲基亚砜)作为块状样品,通过红外光谱、元素分析、质谱分析、电子光谱和磁性能进行了表征。根据角度重叠模型对粉末电子能谱数据进行了分析,得出的结论是该能谱是典型的 D4 对称八面体配位几何,具有微弱的轴向配位场。同时分析了随温度变化的电感和随磁场变化的磁化数据,得出了正的轴向零场分裂参数 D(H = guβSuHu + D[Sz2 - S(S+1)/3]),这与弱轴向配体场一致。单晶 X 射线分析揭示了[Ni(onp)(dmso)(H2O)][BPh4]-dmso(2)和[Ni(onp)(dmf)2][BPh4](3)(dmf = N,N-二甲基甲酰胺)的晶体结构。基于晶体结构的密度泛函理论(DFT)计算表明,[Ni(onp)(dmf)2][BPh4]具有弱轴向配体场的 D4 对称八面体配位几何结构。这项研究还表明了在磁性分析中考虑 g 各向异性的重要性,即使 g 各向异性很小。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Relationship between Structure and Zero-Field Splitting of Octahedral Nickel(II) Complexes with a Low-Symmetric Tetradentate Ligand
Octahedral nickel(II) complexes are among the simplest systems that exhibit zero-field splitting by having two unpaired electrons. For the purpose of clarifying the relationship between structure and zero-field splitting in a low-symmetric system, distorted octahedral nickel(II) complexes were prepared with a tetradentate ligand, 2-[bis(2-methoxyethyl)aminomethyl]-4-nitrophenolate(1−) [(onp)−]. The complex [Ni(onp)(dmso)(H2O)][BPh4]·2dmso (1) (dmso = dimethyl sulfoxide) was characterized as a bulk sample by IR, elemental analysis, mass spectrometry, electronic spectra, and magnetic properties. The powder electronic spectral data were analyzed based on the angular overlap model to conclude that the spectra were typical of D4-symmetric octahedral coordination geometry with a weak axial ligand field. Simultaneous analysis of the temperature-dependent susceptibility and field-dependent magnetization data yielded the positive axial zero-field splitting parameter D (H = guβSuHu + D[Sz2 − S(S + 1)/3]), which was consistent with the weak axial ligand field. Single-crystal X-ray analysis revealed the crystal structures of [Ni(onp)(dmso)(H2O)][BPh4]·dmso (2) and [Ni(onp)(dmf)2][BPh4] (3) (dmf = N,N-dimethylformamide). The density functional theory (DFT) computations based on the crystal structures indicated the D4-symmetric octahedral coordination geometries with weak axial ligand fields. This study also showed the importance of considering g-anisotropy in magnetic analysis, even if g-anisotropy is small.
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来源期刊
ACS Applied Bio Materials
ACS Applied Bio Materials Chemistry-Chemistry (all)
CiteScore
9.40
自引率
2.10%
发文量
464
期刊介绍: ACS Applied Bio Materials is an interdisciplinary journal publishing original research covering all aspects of biomaterials and biointerfaces including and beyond the traditional biosensing, biomedical and therapeutic applications. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrates knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important bio applications. The journal is specifically interested in work that addresses the relationship between structure and function and assesses the stability and degradation of materials under relevant environmental and biological conditions.
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