Academic Journal
Relationship between Structure and Zero-Field Splitting of Octahedral Nickel(II) Complexes with a Low-Symmetric Tetradentate Ligand
| العنوان: | Relationship between Structure and Zero-Field Splitting of Octahedral Nickel(II) Complexes with a Low-Symmetric Tetradentate Ligand |
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| المؤلفون: | Hiroshi Sakiyama, Rin Kimura, Haruto Oomiya, Ryoji Mitsuhashi, Sho Fujii, Katsuhiko Kanaizuka, Mohd. Muddassir, Yuga Tamaki, Eiji Asato, Makoto Handa |
| المصدر: | Magnetochemistry, Vol 10, Iss 5, p 32 (2024) |
| بيانات النشر: | MDPI AG |
| سنة النشر: | 2024 |
| المجموعة: | Directory of Open Access Journals: DOAJ Articles |
| مصطلحات موضوعية: | octahedral nickel(II) complex, crystal structure, density functional theory (DFT), zero-field splitting, magnetic analysis, g -anisotropy, Chemistry, QD1-999 |
| الوصف: | 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)(H 2 O)][BPh 4 ]·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 D 4 -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 = g u β S u H u + D [ S z 2 − 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)(H 2 O)][BPh 4 ]·dmso ( 2 ) and [Ni(onp)(dmf) 2 ][BPh 4 ] ( 3 ) (dmf = N , N -dimethylformamide). The density functional theory (DFT) computations based on the crystal structures indicated the D 4 -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. |
| نوع الوثيقة: | article in journal/newspaper |
| اللغة: | English |
| تدمد: | 2312-7481 |
| Relation: | https://www.mdpi.com/2312-7481/10/5/32; https://doaj.org/toc/2312-7481; https://doaj.org/article/f9853b3a40884979a7879cb7aaeb5cb3 |
| DOI: | 10.3390/magnetochemistry10050032 |
| الاتاحة: | https://doi.org/10.3390/magnetochemistry10050032 https://doaj.org/article/f9853b3a40884979a7879cb7aaeb5cb3 |
| رقم الانضمام: | edsbas.5C822CBB |
| قاعدة البيانات: | BASE |
| تدمد: | 23127481 |
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| DOI: | 10.3390/magnetochemistry10050032 |