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

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

doi:10.1021/jp902735v

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

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

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

16 Citations (Scopus)

Abstract

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 Fe^II 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 (Fe^II_hs)₂[Mo ^IV(CN)₈] · (3-pyCH₂OH)₈ · 3H₂O and (Fe^II_hs) _0.48(Fe^II_ls)_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 Fe^II 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 language	English
Pages (from-to)	15751-15755
Number of pages	5
Journal	Journal of Physical Chemistry C
Volume	113
Issue number	35
DOIs	https://doi.org/10.1021/jp902735v
Publication status	Published - 2009 Sept 3
Externally published	Yes

ASJC Scopus subject areas

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

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10.1021/jp902735v

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@article{b01e3a3daf974c7c94c4a4d5f37816d3,

title = "Extremely gradual spin-crossover phenomenon in a cyano-bridged Fe-Mo bimetallic assembly",

abstract = "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.",

author = "Wataru Kosaka and Hiroko Tokoro and Tomoyuki Matsuda and Kazuhito Hashimoto and Ohkoshi, {Shin Ichi}",

year = "2009",

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doi = "10.1021/jp902735v",

language = "English",

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journal = "Journal of Physical Chemistry C",

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T1 - Extremely gradual spin-crossover phenomenon in a cyano-bridged Fe-Mo bimetallic assembly

AU - Kosaka, Wataru

AU - Tokoro, Hiroko

AU - Matsuda, Tomoyuki

AU - Hashimoto, Kazuhito

AU - Ohkoshi, Shin Ichi

PY - 2009/9/3

Y1 - 2009/9/3

N2 - 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.

AB - 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.

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DO - 10.1021/jp902735v

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JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 35

ER -

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

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