High-Pressure Synthesis and Ferrimagnetic Ordering of the B‑Site-Ordered Cubic Perovskite Pb2FeOsO6

• Published in: Inorganic chemistry Vol. 55; no. 19; pp. 9816 - 9821
• Main Authors: Zhao, Qing, Liu, Min, Dai, Jianhong, Deng, Hongshan, Yin, Yunyu, Zhou, Long, Yang, Junye, Hu, Zhiwei, Agrestini, Stefano, Chen, Kai, Pellegrin, Eric, Valvidares, Manuel, Nataf, Lucie, Baudelet, François, Tjeng, L. H, Yang, Yi-feng, Jin, Changqing, Long, Youwen
• Format: Journal Article
• Language: English
• Published: American Chemical Society 03-10-2016
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.6b01649

Pb2FeOsO6 was prepared for the first time by using high-pressure and high-temperature synthesis techniques. This compound crystallizes into a B-site-ordered double-perovskite structure with cubic symmetry Fm3̅m, where the Fe and Os atoms are orderly distributed with a rock-salt-type manner. Structure refinement shows an Fe–Os antisite occupancy of about 16.6%. Structural analysis and X-ray absorption spectroscopy both demonstrate the charge combination to be Pb2Fe3+Os5+O6. A long-range ferrimagnetic transition is found to occur at about 280 K due to antiferromagnetic interactions between the adjacent Fe3+ and Os5+ spins with a straight (180°) Fe–O–Os bond angle, as confirmed by X-ray magnetic circular-dichroism measurements. First-principles theoretical calculations reveal the semiconducting behavior as well as the Fe3+(↑)­Os5+(↓) antiferromagnetic coupling originating from the superexchange interactions between the half-filled 3d orbitals of Fe and t2g orbitals of Os.