title: Reversible topochemical exsolution of iron in BaFe(2+)2(PO4)2.
abstract: BaFe(2+) 2 (PO4 )2 was recently prepared and identified as the first 2D-Ising ferromagnetic oxide with an original reentrant structural transition driven by high-spin Fe(2+) ions arranged in honeycomb layers. Both long-term air exposure and moderate temperature (T>375 °C) leads to topochemical oxidation into iron-depleted compounds with mixed Fe(2+) /Fe(3+) valence. This process is unique, as the exsolution is effective even from single crystal with preservation of the initial crystallinity, and the structure of the deficient BaFe2-x (PO4 )2 (x<ca. 0.5) is fully ordered for x=2/7 and 1/3 with creation of novel original depleted triangular lattices. Under flowing H2 /Ar, Fe is reincorporated in the structure above 480 °C, as reproduced under the electron beam in a transmission microscope. After Fe exsolution, the insulating ferromagnetic compound turns into an antiferromagnetic semiconductor.
authors.affiliation: Univ. Lille Nord de France, CNRS UMR8181, Unité de Catalyse et de Chimie du Solide, UCCS USTL, F-59655 Villeneuve d'Ascq (France).
authors.forename: Rénald
authors.initials: R
authors.lastname: David
authors.forename: Houria
authors.initials: H
authors.lastname: Kabbour
authors.forename: Dmitry
authors.initials: D
authors.lastname: Filimonov
authors.forename: Marielle
authors.initials: M
authors.lastname: Huvé
authors.forename: Alain
authors.initials: A
authors.lastname: Pautrat
authors.forename: Olivier
authors.initials: O
authors.lastname: Mentré
keywords: barium; exsolution; iron; reversible topochemical reactions; solid-state reactions