Direct Observation of Ordered High-Spin–Low-Spin Intermediate States of an Iron(III) Three-Step Spin-Crossover Complex
Dr. Zhao-Yang Li
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578 Sendai, Japan
These authors contributed equally to this work.
Search for more papers by this authorDr. Hiroyoshi Ohtsu
Division of Advanced Materials Science, Pohang University of Science and Technology (POSTECH), RIST Building 3-3390, 77 Cheongam-Ro, Nam-Gu, Pohang, South Korea
These authors contributed equally to this work.
Search for more papers by this authorDr. Tatsuhiro Kojima
Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043 Japan
Search for more papers by this authorCorresponding Author
Dr. Jing-Wei Dai
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578 Sendai, Japan
Search for more papers by this authorTakefumi Yoshida
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578 Sendai, Japan
Search for more papers by this authorDr. Brian K. Breedlove
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578 Sendai, Japan
Search for more papers by this authorDr. Wei-Xiong Zhang
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, 510275 P.R. China
Search for more papers by this authorDr. Hiroaki Iguchi
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578 Sendai, Japan
Search for more papers by this authorCorresponding Author
Prof. Osamu Sato
Institute for Materials Chemistry and Engineering, Kyushu University, 6-10-1 Hakozaki, Higashiku, Fukuoka, 812-8581 Japan
Search for more papers by this authorProf. Masaki Kawano
Division of Advanced Materials Science, Pohang University of Science and Technology (POSTECH), RIST Building 3-3390, 77 Cheongam-Ro, Nam-Gu, Pohang, South Korea
Search for more papers by this authorCorresponding Author
Prof. Masahiro Yamashita
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578 Sendai, Japan
Search for more papers by this authorDr. Zhao-Yang Li
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578 Sendai, Japan
These authors contributed equally to this work.
Search for more papers by this authorDr. Hiroyoshi Ohtsu
Division of Advanced Materials Science, Pohang University of Science and Technology (POSTECH), RIST Building 3-3390, 77 Cheongam-Ro, Nam-Gu, Pohang, South Korea
These authors contributed equally to this work.
Search for more papers by this authorDr. Tatsuhiro Kojima
Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043 Japan
Search for more papers by this authorCorresponding Author
Dr. Jing-Wei Dai
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578 Sendai, Japan
Search for more papers by this authorTakefumi Yoshida
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578 Sendai, Japan
Search for more papers by this authorDr. Brian K. Breedlove
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578 Sendai, Japan
Search for more papers by this authorDr. Wei-Xiong Zhang
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, 510275 P.R. China
Search for more papers by this authorDr. Hiroaki Iguchi
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578 Sendai, Japan
Search for more papers by this authorCorresponding Author
Prof. Osamu Sato
Institute for Materials Chemistry and Engineering, Kyushu University, 6-10-1 Hakozaki, Higashiku, Fukuoka, 812-8581 Japan
Search for more papers by this authorProf. Masaki Kawano
Division of Advanced Materials Science, Pohang University of Science and Technology (POSTECH), RIST Building 3-3390, 77 Cheongam-Ro, Nam-Gu, Pohang, South Korea
Search for more papers by this authorCorresponding Author
Prof. Masahiro Yamashita
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578 Sendai, Japan
Search for more papers by this authorGraphical Abstract
In quite a state: A neutral mononuclear FeIII complex [FeIII(H-5-Br-thsa-Me)(5-Br-thsa-Me)]⋅H2O (thsa=5-bromosalicylaldehyde methylthiosemicarbazone) exhibited a three-step spin crossover with symmetry breaking and a 14 K hysteresis loop owing to strong cooperativity (see picture). The intermediate spin states showed remarkable long-range 4 HS–2 LS and 2 HS–4 LS spin-state ordering (HS=high-spin, red; LS=low-spin, green).
Abstract
A neutral mononuclear FeIII complex [FeIII(H-5-Br-thsa-Me)(5-Br-thsa-Me)]⋅H2O (1; H2-5-Br-thsa-Me=5-bromosalicylaldehyde methylthiosemicarbazone) was prepared that exhibited a three-step spin-crossover (SCO) with symmetry breaking and a 14 K hysteresis loop owing to strong cooperativity. Two ordered intermediate states of 1 were observed, 4HS–2LS and 2HS–4LS, which exhibited reentrant phase-transition behavior. This study provides a new platform for examining multistability in SCO complexes.
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