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

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

SCI - Chemistry

Research output: Contribution to journal › Article › peer-review

60 Citations (Scopus)

Abstract

A neutral mononuclear Fe^III complex [Fe^III(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. In quite a state: A neutral mononuclear Fe^III complex [Fe^III(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).

Original language	English
Pages (from-to)	5184-5189
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	17
DOIs	https://doi.org/10.1002/anie.201511281
Publication status	Published - 2016 Apr 18

Keywords

cooperativity
iron
multistability
spin crossover
symmetry breaking

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@article{b79b7dc124624f7fb8c56cfc6bd3b830,

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

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. 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).",

keywords = "cooperativity, iron, multistability, spin crossover, symmetry breaking",

author = "Li, {Zhao Yang} and Hiroyoshi Ohtsu and Tatsuhiro Kojima and Dai, {Jing Wei} and Takefumi Yoshida and Breedlove, {Brian K.} and Zhang, {Wei Xiong} and Hiroaki Iguchi and Osamu Sato and Masaki Kawano and Masahiro Yamashita",

note = "Funding Information: Z.Y.L. is grateful for financial support from the Japan Society for the Promotion of Science (JSPS). The X-ray diffraction study with synchrotron radiation was performed at the PFAR (NW2A Beamline) of the High Energy Accelerator Research Organization (KEK; proposal no. 2014G008) and at the Pohang Accelerator Laboratory (Beamline 2D) supported by POSTECH. Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2016",

month = apr,

day = "18",

doi = "10.1002/anie.201511281",

language = "English",

volume = "55",

pages = "5184--5189",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "17",

}

TY - JOUR

T1 - Direct Observation of Ordered High-Spin-Low-Spin Intermediate States of an Iron(III) Three-Step Spin-Crossover Complex

AU - Li, Zhao Yang

AU - Ohtsu, Hiroyoshi

AU - Kojima, Tatsuhiro

AU - Dai, Jing Wei

AU - Yoshida, Takefumi

AU - Breedlove, Brian K.

AU - Zhang, Wei Xiong

AU - Iguchi, Hiroaki

AU - Sato, Osamu

AU - Kawano, Masaki

AU - Yamashita, Masahiro

N1 - Funding Information: Z.Y.L. is grateful for financial support from the Japan Society for the Promotion of Science (JSPS). The X-ray diffraction study with synchrotron radiation was performed at the PFAR (NW2A Beamline) of the High Energy Accelerator Research Organization (KEK; proposal no. 2014G008) and at the Pohang Accelerator Laboratory (Beamline 2D) supported by POSTECH. Publisher Copyright: © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PY - 2016/4/18

Y1 - 2016/4/18

N2 - 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. 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).

AB - 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. 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).

KW - cooperativity

KW - iron

KW - multistability

KW - spin crossover

KW - symmetry breaking

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U2 - 10.1002/anie.201511281

DO - 10.1002/anie.201511281

M3 - Article

AN - SCOPUS:84961266408

SN - 1433-7851

VL - 55

SP - 5184

EP - 5189

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 17

ER -

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

Abstract

Keywords

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