Title
Ba<inf>3</inf>(Cr<inf>0.97(1)</inf>Te<inf>0.03(1)</inf>)<inf>2</inf>TeO<inf>9</inf>: In Search of Jahn-Teller Distorted Cr(II) Oxide
Date Issued
17 October 2016
Access level
metadata only access
Resource Type
journal article
Author(s)
Li M.R.
Deng Z.
Lapidus S.H.
Stephens P.W.
Segre C.U.
Croft M.
Hadermann J.
Walker D.
Greenblatt M.
University of Antwerp
Publisher(s)
American Chemical Society
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.
Start page
10135
End page
10142
Volume
55
Issue
20
Language
English
OCDE Knowledge area
Química inorgánica, Química nuclear
Scopus EID
2-s2.0-84991768826
Source
Inorganic Chemistry
ISSN of the container
00201669
Sponsor(s)
This work was supported by the NSF-DMR-1507252 grant. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions. Use of the Argonne National Laboratory and the Advanced Photon Source is supported by the U.S. Department of Energy, under Contract No. DE-AC02-06CH11357. The authors would like to thank Dr. S. W. Kim at Rutgers Univ. for making a precursor, Ms. J. Hanley at LDEO in Columbia Univ. for making the highpressure assemblies, and Dr. A. Fiege at the American Museum of Natural History in New York City for the assistance of microprobe analyses.
Sources of information:
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