Authors
Makoto Iihoshi, Masato Goto, Kunlang Ji, Rei Watanabe, Daiki Tsurunaga, Patrick M Woodward, Yuichi Shimakawa
Published in
Inorganic chemistry. Jul 12, 2026. Epub Jul 12, 2026.
Abstract
The A-site layer-ordered double perovskites, LnBaFe2O6 with Ln from Pr to Dy and Y, contain mixed and unusually high valent Fe3.5+ ions at high temperatures and upon cooling exhibit successive charge disproportionation transitions to relieve the electronic instability. The first charge disproportionation transition can be represented as 2Fe3.5+ → Fe3+ + Fe4+. This first-order transition is accompanied by a drastic change in structural and magnetic properties, signaling a strong entanglement of charge, spin, and lattice degrees of freedom. The second charge disproportionation transition, 2Fe4+ → Fe3+ + Fe5+, is a second-order-like transition that occurs via intermediate states of LnBa(Fe3+Fe(4-δ)+0.5Fe(4+δ)+0.5)O6. The LnBa(Fe3+1.5Fe5+0.5)O6 ground state is finally stabilized at low temperature. The size of the A-site Ln ion strongly influences the structural and magnetic properties of the compounds. As the size of the Ln3+ ion increases, the temperature of the first charge disproportionation transition decreases almost linearly, while the temperature of the second charge disproportionation transition increases. Consequently, the temperature range over which the intermediate Fe4+ or Fe4+-like Fe(4±δ)+ state is stable narrows. These results demonstrate control over the stability of mixed and unusually high valence ions.
PMID:
42437346
Bibliographic data and abstract were imported from PubMed on 12 Jul 2026.
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