Stepwise spin transition and hysteresis of a tetrameric iron(II) complex, fac-[tris(2-methylimidazol-4-ylmethylidene-n-hexylamine)]iron(II) chloride hexafluorophosphate, assembled by imidazole···chloride hydrogen bonds

Koshiro Nishi; Hiroki Kondo; Takeshi Fujinami; Naohide Matsumoto; Seiichiro Iijima; Malcolm A. Halcrow; Yukinari Sunatsuki; Masaaki Kojima

doi:10.1002/ejic.201201298

Stepwise spin transition and hysteresis of a tetrameric iron(II) complex, fac-[tris(2-methylimidazol-4-ylmethylidene-n-hexylamine)]iron(II) chloride hexafluorophosphate, assembled by imidazole···chloride hydrogen bonds

Koshiro Nishi, Hiroki Kondo, Takeshi Fujinami, Naohide Matsumoto, Seiichiro Iijima, Malcolm A. Halcrow, Yukinari Sunatsuki, Masaaki Kojima

Advanced Science Research Center

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

17 Citations (Scopus)

Abstract

A spin-crossover iron(II) complex, fac-[Fe^II(HL ^n-Hx)₃]Cl·PF₆ (1), that exhibits stepwise spin transition and thermal hysteresis was synthesized by using the ligand 2-methylimidazol- 4-ylmethylidene-n-hexylamine (HLn-Hx). Four complex cations (fac-[Fe^II(HL^n-Hx)₃]²⁺) and four Cl- anions associate through twelve imidazole···Cl- H bonds to give a tetrameric cubane-like assembly, and one PF₆ - anion is encapsulated within the cavity of the cubane. Magnetic susceptibility mea- surements showed a three-step spin transition, and the spincrossover profile became less pronounced as the sweep rate increased. At a sweep rate of 0.5 Kmin^-1, the midpoint temperatures of the three steps are Tc(↓) = 131.2, 144.2, and 154.2 K in the heating mode and Tc(↑) = 116.8, 137.8, and 151.8 K in the cooling mode. The respective thermal hystereses were evaluated to be 14.4, 6.3, and 2.4 K wide.

Original language	English
Pages (from-to)	927-933
Number of pages	7
Journal	European Journal of Inorganic Chemistry
Issue number	5-6
DOIs	https://doi.org/10.1002/ejic.201201298
Publication status	Published - Feb 2013

Keywords

Cubane structure
Hydrogen bonds
Hysteresis
Iron
Spin crossover
Stepwise SCO

ASJC Scopus subject areas

Inorganic Chemistry

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Nishi, K., Kondo, H., Fujinami, T., Matsumoto, N., Iijima, S., Halcrow, M. A., Sunatsuki, Y., & Kojima, M. (2013). Stepwise spin transition and hysteresis of a tetrameric iron(II) complex, fac-[tris(2-methylimidazol-4-ylmethylidene-n-hexylamine)]iron(II) chloride hexafluorophosphate, assembled by imidazole···chloride hydrogen bonds. European Journal of Inorganic Chemistry, (5-6), 927-933. https://doi.org/10.1002/ejic.201201298

Stepwise spin transition and hysteresis of a tetrameric iron(II) complex, fac-[tris(2-methylimidazol-4-ylmethylidene-n-hexylamine)]iron(II) chloride hexafluorophosphate, assembled by imidazole···chloride hydrogen bonds. / Nishi, Koshiro; Kondo, Hiroki; Fujinami, Takeshi; Matsumoto, Naohide; Iijima, Seiichiro; Halcrow, Malcolm A.; Sunatsuki, Yukinari; Kojima, Masaaki.

In: European Journal of Inorganic Chemistry, No. 5-6, 02.2013, p. 927-933.

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

Nishi, K, Kondo, H, Fujinami, T, Matsumoto, N, Iijima, S, Halcrow, MA, Sunatsuki, Y & Kojima, M 2013, 'Stepwise spin transition and hysteresis of a tetrameric iron(II) complex, fac-[tris(2-methylimidazol-4-ylmethylidene-n-hexylamine)]iron(II) chloride hexafluorophosphate, assembled by imidazole···chloride hydrogen bonds', European Journal of Inorganic Chemistry, no. 5-6, pp. 927-933. https://doi.org/10.1002/ejic.201201298

Nishi K, Kondo H, Fujinami T, Matsumoto N, Iijima S, Halcrow MA et al. Stepwise spin transition and hysteresis of a tetrameric iron(II) complex, fac-[tris(2-methylimidazol-4-ylmethylidene-n-hexylamine)]iron(II) chloride hexafluorophosphate, assembled by imidazole···chloride hydrogen bonds. European Journal of Inorganic Chemistry. 2013 Feb;(5-6):927-933. https://doi.org/10.1002/ejic.201201298

Nishi, Koshiro ; Kondo, Hiroki ; Fujinami, Takeshi ; Matsumoto, Naohide ; Iijima, Seiichiro ; Halcrow, Malcolm A. ; Sunatsuki, Yukinari ; Kojima, Masaaki. / Stepwise spin transition and hysteresis of a tetrameric iron(II) complex, fac-[tris(2-methylimidazol-4-ylmethylidene-n-hexylamine)]iron(II) chloride hexafluorophosphate, assembled by imidazole···chloride hydrogen bonds. In: European Journal of Inorganic Chemistry. 2013 ; No. 5-6. pp. 927-933.

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title = "Stepwise spin transition and hysteresis of a tetrameric iron(II) complex, fac-[tris(2-methylimidazol-4-ylmethylidene-n-hexylamine)]iron(II) chloride hexafluorophosphate, assembled by imidazole···chloride hydrogen bonds",

abstract = "A spin-crossover iron(II) complex, fac-[FeII(HL n-Hx)3]Cl·PF6 (1), that exhibits stepwise spin transition and thermal hysteresis was synthesized by using the ligand 2-methylimidazol- 4-ylmethylidene-n-hexylamine (HLn-Hx). Four complex cations (fac-[FeII(HLn-Hx)3]2+) and four Cl- anions associate through twelve imidazole···Cl- H bonds to give a tetrameric cubane-like assembly, and one PF6 - anion is encapsulated within the cavity of the cubane. Magnetic susceptibility mea- surements showed a three-step spin transition, and the spincrossover profile became less pronounced as the sweep rate increased. At a sweep rate of 0.5 Kmin-1, the midpoint temperatures of the three steps are Tc(↓) = 131.2, 144.2, and 154.2 K in the heating mode and Tc(↑) = 116.8, 137.8, and 151.8 K in the cooling mode. The respective thermal hystereses were evaluated to be 14.4, 6.3, and 2.4 K wide.",

keywords = "Cubane structure, Hydrogen bonds, Hysteresis, Iron, Spin crossover, Stepwise SCO",

author = "Koshiro Nishi and Hiroki Kondo and Takeshi Fujinami and Naohide Matsumoto and Seiichiro Iijima and Halcrow, {Malcolm A.} and Yukinari Sunatsuki and Masaaki Kojima",

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AU - Nishi, Koshiro

AU - Kondo, Hiroki

AU - Fujinami, Takeshi

AU - Matsumoto, Naohide

AU - Iijima, Seiichiro

AU - Halcrow, Malcolm A.

AU - Sunatsuki, Yukinari

AU - Kojima, Masaaki

PY - 2013/2

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AB - A spin-crossover iron(II) complex, fac-[FeII(HL n-Hx)3]Cl·PF6 (1), that exhibits stepwise spin transition and thermal hysteresis was synthesized by using the ligand 2-methylimidazol- 4-ylmethylidene-n-hexylamine (HLn-Hx). Four complex cations (fac-[FeII(HLn-Hx)3]2+) and four Cl- anions associate through twelve imidazole···Cl- H bonds to give a tetrameric cubane-like assembly, and one PF6 - anion is encapsulated within the cavity of the cubane. Magnetic susceptibility mea- surements showed a three-step spin transition, and the spincrossover profile became less pronounced as the sweep rate increased. At a sweep rate of 0.5 Kmin-1, the midpoint temperatures of the three steps are Tc(↓) = 131.2, 144.2, and 154.2 K in the heating mode and Tc(↑) = 116.8, 137.8, and 151.8 K in the cooling mode. The respective thermal hystereses were evaluated to be 14.4, 6.3, and 2.4 K wide.

KW - Cubane structure

KW - Hydrogen bonds

KW - Hysteresis

KW - Iron

KW - Spin crossover

KW - Stepwise SCO

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Stepwise spin transition and hysteresis of a tetrameric iron(II) complex, fac-[tris(2-methylimidazol-4-ylmethylidene-n-hexylamine)]iron(II) chloride hexafluorophosphate, assembled by imidazole···chloride hydrogen bonds

Abstract

Keywords

ASJC Scopus subject areas

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