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

IF 4.3 3区材料科学 Q1 ENGINEERING, ELECTRICAL & ELECTRONIC

ACS Applied Electronic Materials Pub Date : 2024-09-26 DOI:10.1039/D4DT02239D

Hajime Yamamoto, Takumi Nishikubo, Shintaro Kobayashi, Kazuki Takahashi, Masaki Azuma, Shogo Kawaguchi and Tadashi Abukawa

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Abstract

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 P 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.

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ZnVO3：一种钛铁矿型氧化钒，含有坚固的 V-V 二聚体

钛铁矿型钒氧化物具有独特的阳离子二聚化行为。在此，我们报告了一种新型钛铁矿型化合物 ZnVO3。多晶 ZnVO3 样品是在 10 GPa 和 1573 K 的条件下合成的。结构中既存在 V-V 二聚体，也存在 Zn-Zn 二聚体（类二聚体位移），它们在每个蜂窝晶格上呈阶梯状排列。值得注意的是，V-V 二聚体可持续到 625 K，超过了其他钛铁矿型钒氧化物中 V-V 二聚体状态的稳定性。磁感应强度测量证实了在二聚体中形成了直接的 V-V 键。Zn2+ 离子在八面体位点的偏心位置，在 Zn-O 共价及其 sp3 性质的驱动下，促进了 Zn-Zn 二聚体般的位移。蜂窝层之间的合作变形进一步加强了 V-V 二聚体。这一发现为通过晶体结构畸变控制晶体化合物中阳离子二聚体的强度提供了启示。

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来源期刊

ACS Applied Electronic Materials Multiple-

CiteScore

7.20

自引率

4.30%

发文量

567