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Crystals 2018, 8(12), 446; https://doi.org/10.3390/cryst8120446

Effect of Transition Metal Substitution on the Charge-Transfer Phase Transition and Ferromagnetism of Dithiooxalato-Bridged Hetero Metal Complexes, (n-C3H7)4N[FeII1−xMnIIxFeIII(dto)3]

1
Department of Chemistry, Faculty of Science Division I, Tokyo University of Science, Tokyo 162-8601, Japan
2
Department of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo, Tokyo 153-8902, Japan
3
Toyota Physical and Chemical Research Institute, Aichi 480-1192, Japan
*
Author to whom correspondence should be addressed.
Received: 2 October 2018 / Revised: 19 November 2018 / Accepted: 21 November 2018 / Published: 28 November 2018
(This article belongs to the Special Issue Synthesis and Applications of New Spin Crossover Compounds)
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Abstract

The dithiooxalato-bridged iron mixed-valence complex (n-C3H7)4N[FeIIFeIII(dto)3] (dto = dithiooxalato) undergoes a novel charge-transfer phase transition (CTPT) accompanied by electron transfer between adjacent FeII and FeIII sites. The CTPT influences the ferromagnetic transition temperature according to the change of spin configuration on the iron sites. To reveal the mechanism of the CTPT, we have synthesized the series of metal-substituted complexes (n-C3H7)4N[FeII1-xMnIIxFeIII(dto)3] (x = 0–1) and investigated their physical properties by means of magnetic susceptibility and dielectric constant measurements. With increasing MnII concentration, x, MnII-substituted complexes show the disappearance of CTPT above x = 0.04, while the ferromagnetic phase remains in the whole range of x. These results are quite different from the physical properties of the ZnII-substituted complex, (n-C3H7)4N[FeII1-xZnIIxFeIII(dto)3], which is attributed to the difference of ion radius as well as the spin states of MnII and ZnII. View Full-Text
Keywords: charge-transfer phase transition; iron mixed-valence complex; hetero metal complex; dithiooxalato ligand; substitution of 3d transition metal ion; ferromagnetism; dielectric response; 57Fe Mössbauer spectroscopy charge-transfer phase transition; iron mixed-valence complex; hetero metal complex; dithiooxalato ligand; substitution of 3d transition metal ion; ferromagnetism; dielectric response; 57Fe Mössbauer spectroscopy
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Enomoto, M.; Ida, H.; Okazawa, A.; Kojima, N. Effect of Transition Metal Substitution on the Charge-Transfer Phase Transition and Ferromagnetism of Dithiooxalato-Bridged Hetero Metal Complexes, (n-C3H7)4N[FeII1−xMnIIxFeIII(dto)3]. Crystals 2018, 8, 446.

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