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Most ABO3 oxides crystalize in the perovskite structure. In responding to the degree of bonding mismatch of A-O versus B-O in the structure, the perovskite can adopt a total of 15 tilting systems of BO6 octahedra. Depending on the charge configurations, i.e. A3+B3+O3, A2+B4+O3, and A1+B5+O3, these complex oxides undergo distinct pathways within the tilting systems as the bond-length mismatch is changed by either the chemical substitution or temperature or pressure. The report of orthorhombic NaOsO3 and the newly synthesized nearly cubic KOsO3 lead to an opportunity for studying the structural distortions in A1+B5+O3 which has only been studied in the d0 systems of AMO3 (A = alkaline, M = Nb, Ta). Here we report the new structural sequence from a cubic perovskite phase to distorted phases as temperature decreases in the solid solution of Na1-xKxOsO3 by synchrotron X-ray powder diffraction; these distorted phases do not belong to the 15 tilting systems. In comparison with the distorted perovskite phases found in the d0 systems of A1+B5+O3 perovskites, the phase transitions with decreasing temperature found in Na1-xKxOsO3 are likely caused by the instabilities of their electronic structures.

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  This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © 2024 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.chemmater.4c00568.

Keyword: KOsO3, Osmate, Perovskite

Date published: 2024-05-16

Publisher: American Chemical Society

Journal:

• CHEMISTRY OF MATERIALS (ISSN: 15205002)

Funding:

• National Science Foundation DMR-2308817
• Japan Society for the Promotion of Science JP22H04601
• Kazuchika Okura Memorial Foundation 2022-11

Manuscript type: Author's version (Accepted manuscript)

MDR DOI:

First published URL: https://pubs.acs.org/doi/10.1021/acs.chemmater.4c00568

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Updated at: 2024-05-27 11:55:03 +0900

Published on MDR: 2025-05-16 08:20:27 +0900