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A new A-site columnar-ordered quadruple perovskite, Gd2CuZnMn4O12, was synthesized by a high-pressure, high-temperature method at 6 GPa and 1500 K. Its structural properties between 100 K and 800 K were investigated by synchrotron powder X-ray diffraction. It has space group Pmmn (No. 59) between 100 K and about 450 K with a layered charge order (CO) of Mn3+ and Mn4+ cations at the perovskite B sites and space group P42/nmc (No. 137) above 475 K with one perovskite B site (having an average manganese oxidation state of +3.5). Anisotropic thermal expansion was observed as the c lattice parameter decreases with increasing temperature above 325 K. Temperature dependence of the unit-cell volume and the lattice parameters and differential scanning calorimetry measurements gave evidence that the CO transition (with TCO = 475 K) is of the second order. Gd2CuZnMn4O12 shows a ferrimagnetic transition below TC = 105 K with an additional decrease of magnetic susceptibilities below about 45 K, probably caused by a gradual increase of the ordered moments on the Gd sublattices coupled antiferromagnetically with the existent ferrimagnetic structure.

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Keyword: A-site columnar-ordered perovskites, quadruple perovskites, high-pressure synthesis, charge ordering

Date published: 2024-01-01

Publisher: Elsevier BV

Journal:

• Journal of Solid State Chemistry (ISSN: 00224596) p. 124543- 124543

Funding:

Manuscript type: Author's version (Accepted manuscript)

MDR DOI: https://doi.org/10.48505/nims.4432

First published URL: https://doi.org/10.1016/j.jssc.2023.124543

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Updated at: 2026-01-01 08:30:12 +0900

Published on MDR: 2026-01-01 08:07:40 +0900