Iron mixed-valence complex, (n-C3H7)4N[FeIIFeIII(dto)3] (dto =C2O2S2), shows a spin-entropy driven phase transition called charge transfer phase transition around 120K and a ferromagnetic transition at 6.5 K. These phase transitions remarkably depend on the hexagonal ring size in two-dimensional honeycomb network structure of [FeIIFeIII(dto)3]∞. In order to control the magnetic properties and the electronic state in the dto-bridged iron mixed-valence system by means of photo-irradiation, we have synthesized a photo-sensitive organic
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