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Na9Bi5Os3O24: A Diamagnetic Oxide Featuring a Pronouncedly Jahn-Teller-Compressed Octahedral Coordination of Osmium(VI)

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Thakur,  Gohil S.
Inorganic Chemistry, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Citation

Thakur, G. S., Reuter, H., Ushakov, A. V., Gallo, G., Nuss, J., Dinnebier, R. E., et al. (2021). Na9Bi5Os3O24: A Diamagnetic Oxide Featuring a Pronouncedly Jahn-Teller-Compressed Octahedral Coordination of Osmium(VI). Angewandte Chemie, International Edition in English, 60(30), 16500-16505. doi:10.1002/anie.202103295.


Cite as: http://hdl.handle.net/21.11116/0000-0008-C288-3
Abstract
The Jahn-Teller (JT) theorem constitutes one of the most fundamental concepts in chemistry. In transition-element chemistry, the 3d(4) and 3d(9) configurations in octahedral complexes are particularly illustrative, where a distortion in local geometry is associated with a reduction of the electronic energy. However, there has been a lasting debate about the fact that the octahedra are found to exclusively elongate. In contrast, for Na9Bi5Os3O24, the octahedron around Os6+(5d(2)) is heavily compressed, lifting the degeneracy of the t(2g) set of 5d orbitals such that in the sense of a JT compression a diamagnetic ground state results. This effect is not forced by structural constraints, the structure offers sufficient space for osmium to shift the apical oxygen atoms to a standard distance. The relevance of these findings is far reaching, since they provide new insights in the hierarchy of perturbations defining ground states of open shell electronic systems. Introduction