Extremely gradual spin-crossover phenomenon in a cyano-bridged Fe-Mo bimetallic assembly

Wataru Kosaka, Hiroko Tokoro, Tomoyuki Matsuda, Kazuhito Hashimoto, Shin Ichi Ohkoshi

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16 Citations (Scopus)


We report a unique type of spin-crossover phenomenon in a three-dimensional (3-D) Fe-Mo network with a cubic structure, Fe2[Mo(CN) 8]·(3-pyCH2OH)8·3H2O (3-py = 3-pyridyl). This compound exhibits an extremely gradual FeII spin-crossover over a wide temperature range, which is more gradual than the crossover according to the Boltzmann distribution. The electronic states at 320 and 50 K are represented as (FeIIhs)2[Mo IV(CN)8] · (3-pyCH2OH)8 · 3H2O and (FeIIhs) 0.48(FeIIls)1.52[Mo IV(CN)8] · (3-pyCH2OH)8 · 3H2O, respectively, where hs and ls denote high spin (S = 2) and low spin (S = 0), respectively. The model calculation based on Slichter-Drickamer's model suggests this extremely gradual spin-crossover can be explained by the contribution of 3-D alternating alignment of hs and ls sites, i.e., -hs-ls-hs-ls-. This system is a strongly correlated system of spin-crossover sites because the spin-crossover FeII sites are directly linked by -NC-Mo-CN-with a high symmetry (FeII sites have one type of symmetry). The elastic interaction due to the volume change in a spin-crossover site isotropically propagates in the whole crystal. Since the CN bridges cannot be disconnected during spin-crossover, a 3-D alternating order of hs and ls sites is considered to be preferable.

Original languageEnglish
Pages (from-to)15751-15755
Number of pages5
JournalJournal of Physical Chemistry C
Issue number35
Publication statusPublished - 2009 Sept 3
Externally publishedYes

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


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