Pressure Effect on Charge-Transfer Phase Transition in a Mixed-Valence Iron Complex, (<i>n</i>-C<sub>3</sub>H<sub>7</sub>)<sub>4</sub>N[Fe<sup>II</sup>Fe<sup>III</sup>(dto)<sub>3</sub>] (dto = C<sub>2</sub>O<sub>2</sub>S<sub>2</sub>)

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  • Kobayashi Yoshihiko
    Department of Applied Physics and Chemistry, The University of Electro-Communications, Chofu, Tokyo 182-8585
  • Itoi Miho
    Graduate School of Arts and Science, The University of Tokyo, Komaba Tokyo 153-8902
  • Kojima Norimichi
    Graduate School of Arts and Science, The University of Tokyo, Komaba Tokyo 153-8902
  • Asai Kichizo
    Department of Applied Physics and Chemistry, The University of Electro-Communications, Chofu, Tokyo 182-8585

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  • Pressure Effect on Charge-Transfer Phase Transition in a Mixed-Valence Iron Complex, (n-C3H7)4N[FeIIFeIII(dto)3] (dto=C2O2S2).

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We have investigated the hydrostatic pressure effect on the charge-transfer phase transition between FeII and FeIII in a mixed-valence iron complex, (n-C3H7)4N[FeIIFeIII(dto)3] (dto = C2O2S2) up to 0.9 GPa. The transition temperature of the charge-transfer phase transition increases almost linearly with increasing applied hydrostatic pressure (∼100 K/GPa), while the ferromagnetic Curie temperature (Tc ∼ 7 K) changes only slightly. The results suggest that the applied hydrostatic pressure stabilizes the low-temperature phase [FeII(S=0)–FeIII(S=5/2)] through the compression of the lattice volume. A phenomenological model taking into account the elastic interactions as a molecular-field explains the characteristics of the charge-transfer phase transition. The analysis of the results of the model calculation suggests that the lattice volume of the high-temperature phase is only about 0.2% larger than that of the low-temperature phase, and a lattice deformation of [FeIIFeIII(dto)3] molecules without the lattice expansion plays an important role in the first-order character of the charge-transfer phase transition.

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