1. Na 9 Bi 5 Os 3 O 24 : A Diamagnetic Oxide Featuring a Pronouncedly Jahn-Teller-Compressed Octahedral Coordination of Osmium(VI).
- Author
-
Thakur GS, Reuter H, Ushakov AV, Gallo G, Nuss J, Dinnebier RE, Streltsov SV, Khomskii DI, and Jansen M
- Abstract
The Jahn-Teller (JT) theorem constitutes one of the most fundamental concepts in chemistry. In transition-element chemistry, the 3d
4 and 3d9 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 Na9 Bi5 Os3 O24 , the octahedron around Os6+ (5d2 ) is heavily compressed, lifting the degeneracy of the t2g 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., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)- Published
- 2021
- Full Text
- View/download PDF