Crystal Structures at Atomic Resolution of the Perovskite-Related GdBaMnFeO5 and Its Oxidized GdBaMnFeO6

Susana García-Martín; Keisuke Manabe; Esteban Urones-Garrote; David Ávila-Brande; Noriya Ichikawa; Yuichi Shimakawa

doi:10.1021/acs.inorgchem.6b02472

Crystal Structures at Atomic Resolution of the Perovskite-Related GdBaMnFeO₅ and Its Oxidized GdBaMnFeO₆

Inorg Chem. 2017 Feb 6;56(3):1412-1417. doi: 10.1021/acs.inorgchem.6b02472. Epub 2017 Jan 9.

Authors

Susana García-Martín¹, Keisuke Manabe², Esteban Urones-Garrote³, David Ávila-Brande¹, Noriya Ichikawa², Yuichi Shimakawa²

Affiliations

¹ Departamento de Química Inorgánica, Facultad de C.C. Químicas, Universidad Complutense , 28040-Madrid, Spain.
² Institute for Chemical Research, Kyoto University , Uji 611-0011 Japan.
³ Centro Nacional de Microscopía Electrónica, Universidad Complutense , 28040-Madrid, Spain.

PMID: 28067507
DOI: 10.1021/acs.inorgchem.6b02472

Abstract

Perovskite-related GdBaMnFeO₅ and the corresponding oxidized phase GdBaMnFeO₆, with long-range layered-type ordering of the Ba and Gd atoms have been synthesized. Oxidation retains the cation ordering but drives a modulation of the crystal structure associated with the incorporation of the oxygen atoms between the Gd layers. Oxidation of GdBaMnFeO₅ increases the oxidation state of Mn from 2+ to 4+, while the oxidation state of Fe remains 3+. Determination of the crystal structure of both GdBaMnFeO₅ and GdBaMnFeO₆ is carried out at atomic resolution by means of a combination of advanced transmission electron microscopy techniques. Crystal structure refinements from synchrotron X-ray diffraction data support the structural models proposed from the TEM data. The oxidation states of the Mn and Fe atoms are evaluated by means of EELS and Mössbauer spectroscopy, which also reveals the different magnetic behavior of these oxides.