V-V Dimerization and Magnetic State of Cobalt Ions in Ilmenite-Type CoVO3

Sachiko Kamiyama; Ikuya Yamada; Masayuki Fukuda; Yuichi Okazaki; Takashi Nakamura; Takumi Nishikubo; Masaki Azuma; Hiroyuki Kimura; Hajime Yamamoto

doi:10.1021/acs.inorgchem.2c00382

V-V Dimerization and Magnetic State of Cobalt Ions in Ilmenite-Type CoVO₃

Inorg Chem. 2022 May 23;61(20):7841-7846. doi: 10.1021/acs.inorgchem.2c00382. Epub 2022 May 9.

Authors

Affiliations

¹ Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira 2-1-1, Aoba-ku, Sendai 980-8577 Japan.
² Department of Materials Science, Graduate School of Engineering, Osaka Prefecture University, Gakuen-cho 1-1, Naka-ku, Sakai, Osaka 599-8531, Japan.
³ Laboratory for Materials and Structures, Tokyo Institute of Technology, Nagatsuta 4259, Midori-ku, Yokohama 226-8503, Japan.
⁴ Kanagawa Institute of Industrial Science and Technology, Shimoimaizumi 705-1, Ebina, Kanagawa 243-0435, Japan.

PMID: 35532118
DOI: 10.1021/acs.inorgchem.2c00382

Abstract

The nature of chemical bonds determines the electronic and magnetic properties of compounds. A metal-metal bonding (V-V dimer) and its effect on the magnetism of ilmenite-type CoVO₃ were studied. Polycrystalline CoVO₃ samples were synthesized using a high-pressure synthesis method. Crystal structure refinement revealed that V-V dimers exist at temperatures below 550 K in the vanadium layers. Co²⁺ in CoVO₃ exhibits an S = 3/2 state, whereas a J_eff = 1/2 state was reported in ilmenite-type CoTiO₃. The existence of V-V dimers reduces the structural symmetry (from R3 to P1), which can change the magnetic ground state.