Suppression of intersite charge transfer in charge-disproportionated perovskite YCu3Fe4O12

Hidenobu Etani, Ikuya Yamada, Kenya Ohgushi, Naoaki Hayashi, Yoshihiro Kusano, Masaichiro Mizumaki, Jungeun Kim, Naruki Tsuji, Ryoji Takahashi, Norimasa Nishiyama, Toru Inoue, Tetsuo Irifune, Mikio Takano

Research output: Contribution to journalArticlepeer-review

26 Citations (Scopus)

Abstract

A novel iron perovskite YCu3Fe4O12 was synthesized under high pressure and high temperature of 15 GPa and 1273 K. Synchrotron X-ray and electron diffraction measurements have demonstrated that this compound crystallizes in the cubic AA′3B4O 12-type perovskite structure (space group Im3Ì..., No. 204) with a lattice constant of a = 7.30764(10) Å at room temperature. YCu 3Fe4O12 exhibits a charge disproportionation of 8Fe3.75+ → 3Fe5+ + 5Fe3+, a ferrimagnetic ordering, and a metal-semiconductor-like transition simultaneously at 250 K, unlike the known isoelectronic compound LaCu3Fe4O 12 that currently shows an intersite charge transfer of 3Cu 2+ + 4Fe3.75+ → 3Cu3+ + 4Fe3+, an antiferromagnetic ordering, and a metal-insulator transition at 393 K. This finding suggests that intersite charge transfer is not the only way of relieving the instability of the Fe3.75+ state in the A3+Cu 2+3Fe3.75+4O12 perovskites. Crystal structure analysis reveals that bond strain, rather than the charge account of the A-site alone, which is enhanced by large A 3+ ions, play an important role in determining which of intersite charge transfer or charge disproportionation is practical.

Original languageEnglish
Pages (from-to)6100-6106
Number of pages7
JournalJournal of the American Chemical Society
Volume135
Issue number16
DOIs
Publication statusPublished - 2013 Apr 24
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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