Crystal structure and structural transition caused by charge-transfer phase transition for iron mixed-valence complex (n-C3H7)4N[FeIIFeIII(dto)3] (dto=C2O2S2)

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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“…[10] In this compound, Fe II -ϱ layers. This structure is common in heterometal oxalato and dithiooxalato complexes.…”

Section: Structural Characterizationmentioning

confidence: 96%

Charge‐Transfer Phase Transition and Ferromagnetism of Iron Mixed‐Valence Complexes (n‐C_nH_2n+1)₄N[Fe^IIFe^III(dto)₃] (n = 3–6; dto = C₂O₂S₂)

et al. 2006

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“…layer stuck alternately along the c axis. The space group is P6 3 , which remains unchanged in whole temperature region at ambient pressure [5]. Figure 1 shows X-ray diffraction profiles under 0.6 GPa on cooling (a) and heating (b).…”

Section: Resultsmentioning

confidence: 99%

Structural Analysis of Iron Mixed-Valence Complex (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto = C₂O₂S₂) under High Pressure

et al. 2007

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Iron mixed-valence complex, (n-C 3 H 7 )4N[Fe II Fe III (dto) 3 ] shows an electron-transfer between Fe(II) and Fe(III) ion accompanied by a spin transition, i.e. a charge-transfer (CT) phase transition at 122.4 K. The pressure dependence of CT phase transition is evaluated by a x-ray structural analysis under high pressure. We report the structural changes of the CT transition under high pressure.

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“…The ðn-C 3 H 7 Þ 4 N þ cation layers are intercalated between two ½Fe II Fe III ðdtoÞ 3 N layers along the c-axis [1]. In this complex, a charge transfer phase transition takes place around 120 K; which is schematically shown in Fig.…”

Section: Introductionmentioning

confidence: 98%

Ferromagnetism of iron mixed-valence complex (n-C3H7)4N[FeIIFeIII(dto)3] (dithiooxalato:dto=C2O2S2)

Itoi

Enomoto

Kojima

2004

Journal of Magnetism and Magnetic Materials

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Crystal structure and structural transition caused by charge-transfer phase transition for iron mixed-valence complex (n-C3H7)4N[FeIIFeIII(dto)3] (dto=C2O2S2)

Cited by 40 publications

References 17 publications

Charge‐Transfer Phase Transition and Ferromagnetism of Iron Mixed‐Valence Complexes (n‐C_nH_2n+1)₄N[Fe^IIFe^III(dto)₃] (n = 3–6; dto = C₂O₂S₂)

Charge‐Transfer Phase Transition and Ferromagnetism of Iron Mixed‐Valence Complexes (n‐C_nH_2n+1)₄N[Fe^IIFe^III(dto)₃] (n = 3–6; dto = C₂O₂S₂)

Structural Analysis of Iron Mixed-Valence Complex (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto = C₂O₂S₂) under High Pressure

Ferromagnetism of iron mixed-valence complex (n-C3H7)4N[FeIIFeIII(dto)3] (dithiooxalato:dto=C2O2S2)

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Crystal structure and structural transition caused by charge-transfer phase transition for iron mixed-valence complex (n-C3H7)4N[FeIIFeIII(dto)3] (dto=C2O2S2)

Cited by 40 publications

References 17 publications

Charge‐Transfer Phase Transition and Ferromagnetism of Iron Mixed‐Valence Complexes (n‐CnH2n+1)4N[FeIIFeIII(dto)3] (n = 3–6; dto = C2O2S2)

Charge‐Transfer Phase Transition and Ferromagnetism of Iron Mixed‐Valence Complexes (n‐CnH2n+1)4N[FeIIFeIII(dto)3] (n = 3–6; dto = C2O2S2)

Structural Analysis of Iron Mixed-Valence Complex (n-C3H7)4N[FeIIFeIII(dto)3] (dto = C2O2S2) under High Pressure

Ferromagnetism of iron mixed-valence complex (n-C3H7)4N[FeIIFeIII(dto)3] (dithiooxalato:dto=C2O2S2)

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Charge‐Transfer Phase Transition and Ferromagnetism of Iron Mixed‐Valence Complexes (n‐C_nH_2n+1)₄N[Fe^IIFe^III(dto)₃] (n = 3–6; dto = C₂O₂S₂)

Charge‐Transfer Phase Transition and Ferromagnetism of Iron Mixed‐Valence Complexes (n‐C_nH_2n+1)₄N[Fe^IIFe^III(dto)₃] (n = 3–6; dto = C₂O₂S₂)

Structural Analysis of Iron Mixed-Valence Complex (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto = C₂O₂S₂) under High Pressure