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
Abstract
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.
期刊介绍:
Magnetochemistry (ISSN 2312-7481) is a unique international, scientific open access journal on molecular magnetism, the relationship between chemical structure and magnetism and magnetic materials. Magnetochemistry publishes research articles, short communications and reviews. Our aim is to encourage scientists to publish their experimental and theoretical results in as much detail as possible. Therefore, there is no restriction on the length of the papers. The full experimental details must be provided so that the results can be reproduced.