TY - JOUR
T1 - Topochemical Synthesis of LiCoF3with a High-Temperature LiNbO3-Type Structure
AU - Matsuo, Yumi
AU - Matsukawa, Yuko
AU - Kitakado, Masahiro
AU - Hasegawa, George
AU - Yoshida, Suguru
AU - Kubonaka, Ryoto
AU - Yoshida, Yuya
AU - Kawasaki, Tatsushi
AU - Kobayashi, Eiichi
AU - Moriyoshi, Chikako
AU - Ohno, Saneyuki
AU - Fujita, Koji
AU - Hayashi, Katsuro
AU - Akamatsu, Hirofumi
N1 - Funding Information:
The authors thank Masatoshi Ishida for the helpful discussion. This research was supported by the Japan Society of the Promotion of Science (JSPS) KAKENHI Grants Nos. JP16H06440, JP17K19172, JP18H01892, JP19H00883, JP21K19027, JP21H05568, JP21K20489, and JP21H04619 and the Murata Science Foundation and Collaborative Research Project of Laboratory for Materials and Structures, Institute of Innovative Research, Tokyo Institute of Technology. This work was also supported by JST, PRESTO Grant Number JPMJPR21QB, Japan. The synchrotron radiation experiments were performed at the BL02B2 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal Nos. 2019A1144, 2019B1251, 2020A1253, and 2021A1473). This work was performed under the approval of the SAGA-LS Advisory Committee (Proposal Nos. 2102005F, 2104033F, and 2109095F). The computation was carried out using the computer resource offered under the category of General Projects by the Research Institute for Information Technology, Kyushu University.
Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/8/1
Y1 - 2022/8/1
N2 - A novel perovskite fluoride, LixCoF3, which has an exceptionally low tolerance factor (0.81), has been synthesized via low-temperature lithium intercalation into a distorted ReO3-type fluoride CoF3using organolithium reagents. Interestingly, this reaction is completed within 15 min at room temperature. Synchrotron X-ray diffractometry and optical second harmonic generation at room temperature have revealed that this compound shows a high-temperature LiNbO3-type structure (space group: R3¯ c) involving Li-Co antisite defects and A-site splitting along the c direction. A-site splitting is consistent with the prediction based on hybrid Hartree-Fock density functional theory calculations. Co-L2,3edge X-ray absorption spectroscopy, as well as bond valence sum analysis, has verified the divalent oxidation state of Co ions in the lithiated phase, suggesting that its composition is close to LiCoF3(x ≈ 1). This compound exhibits a paramagnetic-to-antiferromagnetic transition at 36 K on cooling, accompanied by weak ferromagnetic ordering. The synthetic route based on low-temperature lithiation of metal fluorides host paves the way for obtaining a new LiNbO3-type fluoride family.
AB - A novel perovskite fluoride, LixCoF3, which has an exceptionally low tolerance factor (0.81), has been synthesized via low-temperature lithium intercalation into a distorted ReO3-type fluoride CoF3using organolithium reagents. Interestingly, this reaction is completed within 15 min at room temperature. Synchrotron X-ray diffractometry and optical second harmonic generation at room temperature have revealed that this compound shows a high-temperature LiNbO3-type structure (space group: R3¯ c) involving Li-Co antisite defects and A-site splitting along the c direction. A-site splitting is consistent with the prediction based on hybrid Hartree-Fock density functional theory calculations. Co-L2,3edge X-ray absorption spectroscopy, as well as bond valence sum analysis, has verified the divalent oxidation state of Co ions in the lithiated phase, suggesting that its composition is close to LiCoF3(x ≈ 1). This compound exhibits a paramagnetic-to-antiferromagnetic transition at 36 K on cooling, accompanied by weak ferromagnetic ordering. The synthetic route based on low-temperature lithiation of metal fluorides host paves the way for obtaining a new LiNbO3-type fluoride family.
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U2 - 10.1021/acs.inorgchem.2c01439
DO - 10.1021/acs.inorgchem.2c01439
M3 - Article
C2 - 35861755
AN - SCOPUS:85135419287
SN - 0020-1669
VL - 61
SP - 11746
EP - 11756
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 30
ER -