Chen, Jin-Ming, Chin, Yi-Ying ORCID: 0000-0003-2316-0747, Valldor, Martin, Hu, Zhiwei ORCID: 0000-0003-0324-2227, Lee, Jenn-Min, Haw, Shu-Chih, Hiraoka, Nozomu, Ishii, Hirofumi, Pao, Chih-Wen, Tsuei, Ku-Ding, Lee, Jyh-Fu, Lin, Hong-Ji, Jang, Ling-Yun, Tanaka, Arata ORCID: 0000-0001-8301-8502, Chen, Chien-Te and Tjeng, Liu Hao ORCID: 0000-0002-0595-9312 (2014). A Complete High-to-Low spin state Transition of Trivalent Cobalt Ion in Octahedral Symmetry in SrCo0.5Ru0.5O3-delta. J. Am. Chem. Soc., 136 (4). S. 1514 - 1520. WASHINGTON: AMER CHEMICAL SOC. ISSN 0002-7863

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Abstract

The complex metal oxide SrCo0.5Ru0.5O3-delta possesses a slightly distorted perovskite crystal structure. Its insulating nature infers a well-defined charge distribution, and the six-fold coordinated transition metals have the oxidation states +5 for ruthenium and +3 for cobalt as observed by X-ray spectroscopy. We have discovered that Co3+ ion is purely high-spin at room temperature, which is unique for a Co3+ in an octahedral oxygen surrounding. We attribute this to the crystal field interaction being weaker than the Hund's-rule exchange due to a relatively large mean Co-O distances of 1.98(2) angstrom, as obtained by EXAFS and X-ray diffraction experiments. A gradual high-to-low spin state transition is completed by applying high hydrostatic pressure of up to 40 GPa. Across this spin state transition, the Co K beta emission spectra can be fully explained by a weighted sum of the high-spin and low-spin spectra. Thereby is the much debated intermediate spin state of Co3+ absent in this material. These results allow us to draw an energy diagram depicting relative stabilities of the high-, intermediate-, and low-spin states as functions of the metal-oxygen bond length for a Co3+ ion in an octahedral coordination.

Item Type: Journal Article
Creators:
CreatorsEmailORCIDORCID Put Code
Chen, Jin-MingUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Chin, Yi-YingUNSPECIFIEDorcid.org/0000-0003-2316-0747UNSPECIFIED
Valldor, MartinUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Hu, ZhiweiUNSPECIFIEDorcid.org/0000-0003-0324-2227UNSPECIFIED
Lee, Jenn-MinUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Haw, Shu-ChihUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Hiraoka, NozomuUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Ishii, HirofumiUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Pao, Chih-WenUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Tsuei, Ku-DingUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Lee, Jyh-FuUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Lin, Hong-JiUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Jang, Ling-YunUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Tanaka, ArataUNSPECIFIEDorcid.org/0000-0001-8301-8502UNSPECIFIED
Chen, Chien-TeUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Tjeng, Liu HaoUNSPECIFIEDorcid.org/0000-0002-0595-9312UNSPECIFIED
URN: urn:nbn:de:hbz:38-448102
DOI: 10.1021/ja4114006
Journal or Publication Title: J. Am. Chem. Soc.
Volume: 136
Number: 4
Page Range: S. 1514 - 1520
Date: 2014
Publisher: AMER CHEMICAL SOC
Place of Publication: WASHINGTON
ISSN: 0002-7863
Language: English
Faculty: Unspecified
Divisions: Unspecified
Subjects: no entry
Uncontrolled Keywords:
KeywordsLanguage
PRESSURE; BEHAVIOR; MAGNETORESISTANCE; SPECTROSCOPY; PEROVSKITE; CROSSOVER; LACOO3; OXIDES; BICOO3; LAYERSMultiple languages
Chemistry, MultidisciplinaryMultiple languages
URI: http://kups.ub.uni-koeln.de/id/eprint/44810

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