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The iron mixed‐valence complex, (n‐C3H7)4N[FeIIFeIII(dto)3] (dto = dithiooxalato) shows a charge‐transfer (CT) phase transition at TCT = 122.4 K. In the vicinity of TCT, the spin state changes from FeII (S = 2) – FeIII (S = 1/2) (high‐temperature phase: HTP) to FeII (S = 0) – FeIII (S = 5/2) (low‐temperature phase: LTP) accompanied by a charge transfer between FeII and FeIII. This complex also undergoes a ferromagnetic transition at 7 K in the LTP. In order to investigate the mechanism of the CT phase transition and the ferromagnetism, we have systematically synthesized (n‐CnH2n+1)4N[FeIIFeIII(dto)3] (n = 3–6), and have investigated their physical properties by magnetic susceptibility, powder X‐ray diffraction measurements, and ESR spectroscopy. The compounds (n‐CnH2n+1)4N[FeIIFeIII(dto)3] (n = 3–6) display ferromagnetic phase transitions at 7 K, 7 K (& 13 K), 19.5 K, and 22 K, respectively. For n = 3 and 4, the CT phase transitions take place at TCT ≈ 120 K and TCT ≈ 140 K, respectively. For n = 5 and 6, on the other hand, the CT phase transition does not occur, and the spin configuration of FeII (S = 2) and FeIII (S = 1/2) corresponding to the HTP for n = 3 and 4 is stable between 2 K and 300 K. The cation size of (n‐CnH2n+1)4N+ (n = 3–6) acts as an effective internal pressure which induces the CT phase transition and the ferromagnetic ordering in the [FeIIFeIII(dto)3]–∞ layer. We also discuss the mechanism of the CT phase transition and the ferromagnetism induced by the charge‐transfer interaction between FeII and FeIII. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Iron mixed-valence complex, (n-C(3)H(7))(4)N[Fe(II)Fe(III)(dto)(3)](dto = C(2)O(2)S(2)), shows a spin entropy-driven phase transition called charge transfer phase transition in [Fe(II)Fe(III)(dto)(3)](-)(infinity) around 120 K and a ferromagnetic transition at 7 K. These phase transitions remarkably depend on the hexagonal ring size in the two-dimensional honeycomb network structure of [Fe(II)Fe(III)(dto)(3)](-)(infinity). In order to control the magnetic properties and the electronic state in the dto-bridged iron mixed-valence system by means of photoirradiation, we have synthesized a photosensitive organic-inorganic hybrid system, (SP)[Fe(II)Fe(III)(dto)(3)](SP = spiropyran), and investigated the photoinduced effect on the magnetic properties. Upon UV irradiation at 350 nm, a broad absorption band between 500 and 600 nm appears and continuously increases with the photoirradiation time, which implies that the UV irradiation changes the structure of spiropyran from the closed form to the open one in solid state. The photochromism in spiropyran changes the ferromagnetic transition temperature from 5 to 22 K and the coercive force from 1400 to 6000 Oe at 2 K. In this process, the concerted phenomenon coupled with the charge transfer phase transition in [Fe(II)Fe(III)(dto)(3)](-)(infinity) and the photoisomerization of spiropyran is realized.