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

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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.

Original languageEnglish
Pages (from-to)927-933
Number of pages7
JournalEuropean Journal of Inorganic Chemistry
Issue number5-6
DOIs
Publication statusPublished - Feb 1 2013

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Keywords

  • Cubane structure
  • Hydrogen bonds
  • Hysteresis
  • Iron
  • Spin crossover
  • Stepwise SCO

ASJC Scopus subject areas

  • Inorganic Chemistry

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