Effect of Transition Metal Substitution on the Charge-Transfer Phase Transition and Ferromagnetism of Dithiooxalato-Bridged Hetero Metal Complexes, (<i>n</i>-C₃H₇)₄N[Fe^II_1−<i>x</i>Mn^II<i>_x</i>Fe^III(dto)₃]

• Main Authors: Masaya Enomoto, Hiromichi Ida, Atsushi Okazawa, Norimichi Kojima
• Format: Article
• Language: English
• Published: MDPI AG 2018-11-01
• Series: Crystals
• Subjects: 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
• Online Access: https://www.mdpi.com/2073-4352/8/12/446

The dithiooxalato-bridged iron mixed-valence complex (<i>n</i>-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto = dithiooxalato) undergoes a novel charge-transfer phase transition (CTPT) accompanied by electron transfer between adjacent Fe^II and Fe^III 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 (<i>n-</i>C₃H₇)₄N[Fe^II_1-<i>x</i>Mn^II<i>_x</i>Fe^III(dto)₃] (<i>x</i> = 0&#8315;1) and investigated their physical properties by means of magnetic susceptibility and dielectric constant measurements. With increasing Mn^II concentration, <i>x</i>, Mn^II-substituted complexes show the disappearance of CTPT above <i>x</i> = 0.04, while the ferromagnetic phase remains in the whole range of <i>x</i>. These results are quite different from the physical properties of the Zn^II-substituted complex, (<i>n-</i>C₃H₇)₄N[Fe^II_1-<i>x</i>Zn^II<i>_x</i>Fe^III(dto)₃], which is attributed to the difference of ion radius as well as the spin states of Mn^II and Zn^II.