Crystal Chemistry, Optical Spectroscopy and Crystal Field Calculations of Co 3 TeO 6 and Solid Solutions Co 3– x Zn x TeO 6
[1];
- Institut für Mineralogie und Kristallographie Faculty of Geosciences, Geography and Astronomy University of Vienna Althanstr. 14, A‐ 1090 Vienna Austria
- Institute for Chemical Technology and Analytics Division of Structural Chemistry TU Wien Getreidemarkt 9/164‐SC, A ‐1060 Vienna Austria
- Department of Engineering Sciences Solid State Physics. Angstrom Laboratory Uppsala University P.O. Box 534 SE‐751 21 Uppsala Sweden, Karpov' Institute of Physical Chemistry Vorontsovo pole st., 10 105064 Moscow Russia
- Karpov' Institute of Physical Chemistry Vorontsovo pole st., 10 105064 Moscow Russia, ChemMatCARS beamline The University of Chicago Advanced Photon Source 60439 Argonne Illinois United States
- ChemMatCARS beamline The University of Chicago Advanced Photon Source 60439 Argonne Illinois United States
Solid solutions Co 3– x Zn x TeO 6 ( x = 0–3) were prepared both in polycrystalline and single‐crystalline form using solid state reactions and chemical vapour transport reactions, respectively. Miscibility between the isotypic end members was established over the complete range ( C 2/ c, Z = 12, a ≈ 14.85, b ≈ 8.83, c ≈ 10.34 Å, β ≈ 93°). Crystal structure determinations, performed on basis of single crystal laboratory X‐ray (at 295 K) and synchrotron (at 10 and 100 K) data of Co 3 TeO 6 and selected solid solutions, revealed no structural phase transition and allowed a detailed insight into the Co → Zn substitution mechanism. The coordination polyhedra of the five crystallographically independent M 2+ cations are distorted octahedra (for three cations), one distorted tetrahedron and one distorted square pyramid. With increasing Zn content the polyhedral distortions increase, and the preference of the Zn 2+ cation for the tetrahedral coordination becomes distinctive. Optical absorption and diffuse reflectance spectroscopy reveal extraordinary strong crystal field absorption effects, over wide x ranges predominantly governed by Co 2+ in the single tetrahedral and one strongly acentric distorted octahedral site. Superposition Model crystal field calculations yield intrinsic and power‐law exponent parameters in general agreement with previous data for Co 2+ . The five cation sites show comparatively high crystal field strengths at generally very low interelectronic repulsion parameters, indicating prominent covalent contribution to Co–O bonding in Co 3– x Zn x TeO 6 solid solutions.
- Sponsoring Organization:
- USDOE
- Grant/Contract Number:
- AC02-06CH11357
- OSTI ID:
- 1476655
- Journal Information:
- European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry Journal Issue: 38 Vol. 2018; ISSN 1434-1948
- Publisher:
- Wiley Blackwell (John Wiley & Sons)Copyright Statement
- Country of Publication:
- Germany
- Language:
- English
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