Wide-Range Tuning of the Mo Oxidation State in La1-xSrxFe2/3Mo1/3O3 Perovskites

La1–xSrxFe2/3Mo1/3O3 (0 ≤ x ≤ 1) perovskites allow exceptionally wide tuning of the Mo oxidation state from +3 (x = 0) to +6 (x = 1) with the FeIII oxidation state virtually unchanged. The end members of this series show antiferromagnetic ordering in LaFe2/3Mo1/3O3 at TN = 520 K and ferrimagnetic or...

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Published in:European journal of inorganic chemistry 2016-06, Vol.2016 (18), p.2942-2951
Main Authors: Istomin, Sergey Ya, Chernova, Varvara V., Antipov, Evgeny V., Lobanov, Maxim V., Bobrikov, Ivan A., Yushankhai, Viktor Yu, Balagurov, Anatoly M., Hsu, K. Y., Lin, J. -Y., Chen, J. M., Lee, J. F., Volkova, Olga S., Vasiliev, Alexander N.
Format: Article
Language:English
Subjects:
Antiferromagnetism
Insulators
Iron
Magnetic properties
Molybdenum
Order disorder
Perovskite phases
Perovskites
Saturation (magnetic)
Tuning
Valence
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Summary:La1–xSrxFe2/3Mo1/3O3 (0 ≤ x ≤ 1) perovskites allow exceptionally wide tuning of the Mo oxidation state from +3 (x = 0) to +6 (x = 1) with the FeIII oxidation state virtually unchanged. The end members of this series show antiferromagnetic ordering in LaFe2/3Mo1/3O3 at TN = 520 K and ferrimagnetic ordering in SrFe2/3Mo1/3O3 at TC = 420 K. The crucial role of electron correlations in the Mo 4d shell suggests that LaFe2/3Mo1/3O3 with a half‐filled band is a Mott insulator, whereas SrFe2/3Mo1/3O3 is a band insulator. In both cases, the magnetic structure is dictated by antiferromagnetic superexchange between localized magnetic moments. At intermediate compositions, an interplay of antiferromagnetic‐superexchange and double‐exchange interactions results in nonmonotonous variations of both the magnetic‐ordering temperature and saturation magnetization. La1–xSrxFe2/3Mo1/3O3 perovskites allow wide tuning of the Mo oxidation state from +3 (x = 0) to +6 (x = 1) with the FeIII oxidation state virtually unchanged. The magnetic properties vary between antiferromagnetic (AFM) for x = 0 to ferromagnetic (FIM) for x = 1.0.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.201600020