Ba4KFe3O9: a novel ferrite containing discrete 6-membered rings of corner-sharing FeO4 tetrahedra

Inorg Chem. 2011 Oct 17;50(20):10310-8. doi: 10.1021/ic201374g. Epub 2011 Sep 12.

Abstract

Single crystals of a new iron-containing oxide, Ba(4)KFe(3)O(9), were grown from a hydroxide melt, and the crystal structure was determined by single-crystal X-ray diffraction. This ferrite represents the first complex oxide containing isolated 6-membered rings of corner-sharing FeO(4) tetrahedra. Mössbauer measurements are indicative of two tetrahedral high-spin Fe(3+) coordination environments. The observed magnetic moment (~3.9 μ(B)) at 400 K is significantly lower than the calculated spin-only (~5.2 μ(B)) value, indicating the presence of strong antiferromagnetic interactions in the oxide. Our density functional theory calculations confirm the strong antiferromagnetic coupling between adjacent Fe(3+) sites within each 6-membered ring and estimate the nearest-neighbor spin-exchange integral as ~200 K; next-nearest-neighbor interactions are shown to be negligible. The lower than expected effective magnetic moment for Ba(4)KFe(3)O(9) calculated from χT data is explained as resulting from the occupation of lower-lying magnetic states in which more spins are paired. X-band (9.5 GHz) electron paramagnetic resonance (EPR) spectra of a powder sample consist of a single line at g ~ 2.01 that is characteristic of Fe(3+) ions in a tetrahedral environment, thus confirming the Mössbauer results. Further analysis of the EPR line shape reveals the presence of two types of Fe(6) magnetic species with an intensity ratio of ~1:9. Both species have Lorentzian line shapes and indistinguishable g factors but differ in their peak-to-peak line widths (δB(pp)). The line-width ratio δB(pp)(major)/δB(pp)(minor) ~ 3.6 correlates well with the ratio of the Weiss constants, θ(minor)/θ(major) ~ 4.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Boron Compounds / chemistry*
  • Crystallography, X-Ray
  • Electron Spin Resonance Spectroscopy
  • Ferric Compounds / chemistry*
  • Hot Temperature
  • Iron Compounds / chemistry*
  • Magnetic Phenomena
  • Models, Molecular
  • Molecular Conformation
  • Oxides / chemistry*
  • Quantum Theory
  • Spectroscopy, Mossbauer

Substances

  • Boron Compounds
  • Ferric Compounds
  • Iron Compounds
  • Oxides
  • ferrite