ZnVO3: an ilmenite-type vanadium oxide hosting robust V–V dimers

• Published in: Dalton transactions : an international journal of inorganic chemistry 2024-10, Vol.53 (39), p.16195-16201
• Main Authors: Yamamoto, Hajime, Nishikubo, Takumi, Kobayashi, Shintaro, Takahashi, Kazuki, Azuma, Masaki, Kawaguchi, Shogo, Abukawa, Tadashi
• Format: Article
• Language: English
• Subjects: Cations; Cooperative control; Crystal structure; Dimerization; Dimers; Ilmenite; Magnetic permeability; Molecular structure; Position measurement; Vanadium oxides
• ISSN: 1477-9226; 1477-9234; 1477-9234
• DOI: 10.1039/d4dt02239d

Ilmenite-type vanadium oxides exhibit a distinctive cation-dimerization behavior. Here, we report a novel ilmenite-type compound, ZnVO3. Polycrystalline ZnVO3 samples are synthesized under conditions of 10 GPa and 1573 K. The obtained sample crystallizes in the triclinic P1 space group. Both V–V and Zn–Zn dimers (dimer-like displacement) are present in the structure, arranged in a ladder-like pattern on each honeycomb lattice. Notably, the V–V dimer persists up to 625 K, surpassing the stability of the V–V dimer state in other ilmenite-type vanadium oxides. Magnetic susceptibility measurements corroborate the formation of direct V–V bond in the dimer. The off-centered position of the Zn2+ ion at the octahedral site, driven by Zn–O covalency and its sp3 nature, promotes the Zn–Zn dimer-like displacement. Cooperative distortions between honeycomb layers further reinforce the V–V dimers. This finding offers insights into controlling cation-dimer strength in crystalline compounds via crystal structure distortions.