Ba3(Cr0.97(1)Te0.03(1))2TeO9: In Search of Jahn-Teller Distorted Cr(II) Oxide

Man Rong Li, Zheng Deng, Saul H. Lapidus, Peter W. Stephens, Carlo U. Segre, Mark Croft, Robert Paria Sena, Joke Hadermann, David Walker, Martha Greenblatt

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Abstract

A novel 6H-type hexagonal perovskite Ba3(Cr0.97(1)Te0.03(1))2TeO9 was prepared at high pressure (6 GPa) and temperature (1773 K). Both transmission electron microscopy and synchrotron powder X-ray diffraction data demonstrate that Ba3(Cr0.97(1)Te0.03(1))2TeO9 crystallizes in P63/mmc with face-shared (Cr0.97(1)Te0.03(1))O6 octahedral pairs interconnected with TeO6 octahedra via corner-sharing. Structure analysis shows a mixed Cr2+/Cr3+ valence state with ∼10% Cr2+. The existence of Cr2+ in Ba3(Cr2+0.10(1)Cr3+0.87(1)Te6+0.03)2TeO9 is further evidenced by X-ray absorption near-edge spectroscopy. Magnetic properties measurements show a paramagnetic response down to 4 K and a small glassy-state curvature at low temperature. In this work, the octahedral Cr2+O6 component is stabilized in an oxide material for the first time; the expected Jahn-Teller distortion of high-spin (d4) Cr2+ is not found, which is attributed to the small proportion of Cr2+ (∼10%) and the face-sharing arrangement of CrO6 octahedral pairs, which structurally disfavor axial distortion.

Original languageEnglish (US)
Pages (from-to)10135-10142
Number of pages8
JournalInorganic Chemistry
Volume55
Issue number20
DOIs
StatePublished - Oct 17 2016

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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