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Title
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Disproportionation of in the topochemically reduced oxide LaSrCoRuO₅
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Author
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Abstract
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| Complex transition-metal oxides exhibit a wide variety of chemical and physical properties which are a strong function the local electronic states of the transition-metal centres, as determined by a combination of metal oxidation state and local coordination environment. Topochemical reduction of the double perovskite oxide, LaSrCoRuO6, using Zr, yields LaSrCoRuO5. This reduced phase contains an ordered array of apex-linked square-based pyramidal Ru3+O5, square-planar Co1+O4 and octahedral Co3+O6 units, consistent with the coordination-geometry driven disproportionation of Co2+. Coordination-geometry driven disproportionation of d(7) transition-metal cations (e.g. Rh2+, Pd3+, Pt3+) is common in complex oxides containing 4d and 5d metals. However, the weak ligand field experienced by a 3d transition-metal such as cobalt leads to the expectation that d(7+) Co2+ should be stable to disproportionation in oxide environments, so the presence of Co1+O4 and Co3+O6 units in LaSrCoRuO5 is surprising. Low-temperature measurements indicate LaSrCoRuO5 adopts a ferromagnetically ordered state below 120 K due to couplings between S=(1)/(2) Ru3+ and S=1 Co1+. |
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Language
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English
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Source (journal)
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Angewandte Chemie: international edition in English. - Weinheim
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Publication
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Weinheim
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Wiley-v c h verlag gmbh
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2024
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ISSN
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1433-7851
0570-0833
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DOI
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10.1002/ANIE.202313067
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Volume/pages
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63
:6
(2024)
, p. 1-5
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Article Reference
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e202313067
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ISI
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001136579700001
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Pubmed ID
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38085493
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Full text (Publisher's DOI)
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Full text (open access)
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