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

Research output: Contribution to journalArticlepeer-review

9 Citations (Scopus)

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 languageEnglish
Pages (from-to)8989-8996
Number of pages8
JournalInorganic Chemistry
Volume51
Issue number16
DOIs
Publication statusPublished - 2012 Aug 20
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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