Synthesis, structure and magnetic properties of V4O9-A missing link in binary vanadium oxides

Satoshi Yamazaki, Chang Li, Kenji Ohoyama, Masakazu Nishi, Masaki Ichihara, Hiroaki Ueda, Yutaka Ueda

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20 Citations (Scopus)

Abstract

V4O9: A missing link of Wadsley phases has been successfully synthesized by using sulfur as a reducing agent at a low temperature and its structure has been determined by combining electron, X-ray and neutron diffractions. V4O9 has an orthorhombic Cmcm structure and the lattice parameters are a=10.356(2) Å, b=8.174(1) Å and c=16.559(3) Å at room temperature. The structure is composed of shared edges and corners of three types of polyhedra; a VO6 distorted octahedron, a VO5 pyramid and a VO4 tetrahedron. The structure of V4O9 is very similar to that of vanadyl pyrophosphate (VO)2P2O7 which has PO4 tetrahedra instead of VO4 tetrahedra. This indicates that V4O9 is a salt of pyro-ion [V2O7]4-; (VO)2V2O7. The magnetic properties of V4O9 have been investigated by magnetic susceptibility, high-field magnetization and inelastic neutron scattering measurements. V4O9 is a quantum spin system with a spin-gapped ground state. The excitation gap between the singlet ground state and the excited triplet state is approximately 73 K. The magnetic susceptibility behavior suggests that V4O9 is a spin-1/2 dimer system with significant interdimer interactions, as opposed to (VO)2P2O7, which is an alternating spin-1/2 chain system. This difference is thought to be due to the fact that VO4-mediated interactions are considerably weaker than PO4-mediated interactions.

Original languageEnglish
Pages (from-to)1496-1503
Number of pages8
JournalJournal of Solid State Chemistry
Volume183
Issue number7
DOIs
Publication statusPublished - 2010 Jul 1

Keywords

  • Binary vanadium oxide
  • Magnetic properties
  • Synthesis and crystal structure
  • VO

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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    Yamazaki, S., Li, C., Ohoyama, K., Nishi, M., Ichihara, M., Ueda, H., & Ueda, Y. (2010). Synthesis, structure and magnetic properties of V4O9-A missing link in binary vanadium oxides. Journal of Solid State Chemistry, 183(7), 1496-1503. https://doi.org/10.1016/j.jssc.2010.04.007