Direct Observation of Ordered High-Spin-Low-Spin Intermediate States of an Iron(III) Three-Step Spin-Crossover Complex

Zhao-Yang Li; Hiroyoshi Ohtsu; Tatsuhiro Kojima; Jing-Wei Dai; Takefumi Yoshida; Brian K Breedlove; Wei-Xiong Zhang; Hiroaki Iguchi; Osamu Sato; Masaki Kawano; Masahiro Yamashita

doi:10.1002/anie.201511281

Direct Observation of Ordered High-Spin-Low-Spin Intermediate States of an Iron(III) Three-Step Spin-Crossover Complex

Angew Chem Int Ed Engl. 2016 Apr 18;55(17):5184-9. doi: 10.1002/anie.201511281. Epub 2016 Mar 17.

Authors

Affiliations

¹ Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578, Sendai, Japan.
² Division of Advanced Materials Science, Pohang University of Science and Technology (POSTECH), RIST Building 3-3390, 77 Cheongam-Ro, Nam-Gu, Pohang, South Korea.
³ Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043, Japan.
⁴ Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578, Sendai, Japan. jingweiii@gmail.com.
⁵ MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, 510275, P.R. China.
⁶ Institute for Materials Chemistry and Engineering, Kyushu University, 6-10-1 Hakozaki, Higashiku, Fukuoka, 812-8581, Japan. sato@cm.kyushu-u.ac.jp.
⁷ Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, 980-8578, Sendai, Japan. yamasita.m@gmail.com.

PMID: 26991042
DOI: 10.1002/anie.201511281

Abstract

A neutral mononuclear Fe(III) complex [Fe(III) (H-5-Br-thsa-Me)(5-Br-thsa-Me)]⋅H2 O (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.

Keywords: cooperativity; iron; multistability; spin crossover; symmetry breaking.

Publication types

Research Support, Non-U.S. Gov't