Effect of nonmagnetic substitution on the magnetic properties and charge-transfer phase transition of an iron mixed-valence complex, (n- C 3H 7) 4N[Fe IIFe III(dto) 3] (dto = C 2O 2S 2)

Hiromichi Ida; Atsushi Okazawa; Norimichi Kojima; Ryo Shimizu; Yasuhiro Yamada; Masaya Enomoto

doi:10.1021/ic3010954

Effect of nonmagnetic substitution on the magnetic properties and charge-transfer phase transition of an iron mixed-valence complex, (n- C ₃H ₇) ₄N[Fe ^IIFe ^III(dto) ₃] (dto = C ₂O ₂S ₂)

Hiromichi Ida, Atsushi Okazawa, Norimichi Kojima, Ryo Shimizu, Yasuhiro Yamada, Masaya Enomoto^*

^*Corresponding author for this work

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Abstract

The iron mixed-valence complex (n-C ₃H ₇) ₄N[Fe ^IIFe ^III(dto) ₃] exhibits a novel type of phase transition called charge-transfer phase transition (CTPT), where the thermally induced electron transfer between Fe ^II and Fe ^III occurs reversibly at ∼120 K, in addition to the ferromagnetic phase transition at T _C = 7 K. To investigate the mechanism of the CTPT, we have synthesized a series of magnetically diluted complexes (n-C ₃H ₇) ₄N[Fe ^II _1-xZn ^II _xFe ^III(dto) ₃] (dto = C ₂O ₂S ₂; x = 0-1), and carried out magnetic susceptibility and dielectric constant measurements and ⁵⁷Fe Mössbauer spectroscopy. With increasing Zn ^II concentration (x), the CTPT is gradually suppressed and disappears at x ≈ 0.13. On the other hand, the ferromagnetic transition temperature (T _C) is initially enhanced from 7 K to 12 K between x = 0.00 and 0.05, despite the nonmagnetic nature of Zn ^II ions, and then it decreases monotonically from 12 K to 3 K with increasing Zn ^II concentration. This anomalous dependence of T _C on Zn ^II concentration is related to a change in the spin configuration of the ferromagnetic state caused by the partial suppression of the CTPT.

Original language	English
Pages (from-to)	8989-8996
Number of pages	8
Journal	Inorganic Chemistry
Volume	51
Issue number	16
DOIs	https://doi.org/10.1021/ic3010954
Publication status	Published - 2012 Aug 20
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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Effect of nonmagnetic substitution on the magnetic properties and charge-transfer phase transition of an iron mixed-valence complex, (n- C ₃H ₇) ₄N[Fe ^IIFe ^III(dto) ₃] (dto = C ₂O ₂S ₂). / Ida, Hiromichi; Okazawa, Atsushi; Kojima, Norimichi et al.

In: Inorganic Chemistry, Vol. 51, No. 16, 20.08.2012, p. 8989-8996.

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

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title = "Effect of nonmagnetic substitution on the magnetic properties and charge-transfer phase transition of an iron mixed-valence complex, (n- C 3H 7) 4N[Fe IIFe III(dto) 3] (dto = C 2O 2S 2)",

abstract = "The iron mixed-valence complex (n-C 3H 7) 4N[Fe IIFe III(dto) 3] exhibits a novel type of phase transition called charge-transfer phase transition (CTPT), where the thermally induced electron transfer between Fe II and Fe III occurs reversibly at ∼120 K, in addition to the ferromagnetic phase transition at T C = 7 K. To investigate the mechanism of the CTPT, we have synthesized a series of magnetically diluted complexes (n-C 3H 7) 4N[Fe II 1-xZn II xFe III(dto) 3] (dto = C 2O 2S 2; x = 0-1), and carried out magnetic susceptibility and dielectric constant measurements and 57Fe M{\"o}ssbauer spectroscopy. With increasing Zn II concentration (x), the CTPT is gradually suppressed and disappears at x ≈ 0.13. On the other hand, the ferromagnetic transition temperature (T C) is initially enhanced from 7 K to 12 K between x = 0.00 and 0.05, despite the nonmagnetic nature of Zn II ions, and then it decreases monotonically from 12 K to 3 K with increasing Zn II concentration. This anomalous dependence of T C on Zn II concentration is related to a change in the spin configuration of the ferromagnetic state caused by the partial suppression of the CTPT.",

author = "Hiromichi Ida and Atsushi Okazawa and Norimichi Kojima and Ryo Shimizu and Yasuhiro Yamada and Masaya Enomoto",

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T1 - Effect of nonmagnetic substitution on the magnetic properties and charge-transfer phase transition of an iron mixed-valence complex, (n- C 3H 7) 4N[Fe IIFe III(dto) 3] (dto = C 2O 2S 2)

AU - Ida, Hiromichi

AU - Okazawa, Atsushi

AU - Kojima, Norimichi

AU - Shimizu, Ryo

AU - Yamada, Yasuhiro

AU - Enomoto, Masaya

PY - 2012/8/20

Y1 - 2012/8/20

N2 - The iron mixed-valence complex (n-C 3H 7) 4N[Fe IIFe III(dto) 3] exhibits a novel type of phase transition called charge-transfer phase transition (CTPT), where the thermally induced electron transfer between Fe II and Fe III occurs reversibly at ∼120 K, in addition to the ferromagnetic phase transition at T C = 7 K. To investigate the mechanism of the CTPT, we have synthesized a series of magnetically diluted complexes (n-C 3H 7) 4N[Fe II 1-xZn II xFe III(dto) 3] (dto = C 2O 2S 2; x = 0-1), and carried out magnetic susceptibility and dielectric constant measurements and 57Fe Mössbauer spectroscopy. With increasing Zn II concentration (x), the CTPT is gradually suppressed and disappears at x ≈ 0.13. On the other hand, the ferromagnetic transition temperature (T C) is initially enhanced from 7 K to 12 K between x = 0.00 and 0.05, despite the nonmagnetic nature of Zn II ions, and then it decreases monotonically from 12 K to 3 K with increasing Zn II concentration. This anomalous dependence of T C on Zn II concentration is related to a change in the spin configuration of the ferromagnetic state caused by the partial suppression of the CTPT.

AB - The iron mixed-valence complex (n-C 3H 7) 4N[Fe IIFe III(dto) 3] exhibits a novel type of phase transition called charge-transfer phase transition (CTPT), where the thermally induced electron transfer between Fe II and Fe III occurs reversibly at ∼120 K, in addition to the ferromagnetic phase transition at T C = 7 K. To investigate the mechanism of the CTPT, we have synthesized a series of magnetically diluted complexes (n-C 3H 7) 4N[Fe II 1-xZn II xFe III(dto) 3] (dto = C 2O 2S 2; x = 0-1), and carried out magnetic susceptibility and dielectric constant measurements and 57Fe Mössbauer spectroscopy. With increasing Zn II concentration (x), the CTPT is gradually suppressed and disappears at x ≈ 0.13. On the other hand, the ferromagnetic transition temperature (T C) is initially enhanced from 7 K to 12 K between x = 0.00 and 0.05, despite the nonmagnetic nature of Zn II ions, and then it decreases monotonically from 12 K to 3 K with increasing Zn II concentration. This anomalous dependence of T C on Zn II concentration is related to a change in the spin configuration of the ferromagnetic state caused by the partial suppression of the CTPT.

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Effect of nonmagnetic substitution on the magnetic properties and charge-transfer phase transition of an iron mixed-valence complex, (n- C ₃H ₇) ₄N[Fe ^IIFe ^III(dto) ₃] (dto = C ₂O ₂S ₂)

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