Na9Bi5Os3O24: A Diamagnetic Oxide Featuring a Pronouncedly Jahn–Teller-Compressed Octahedral Coordination of Osmium(VI)
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Contributors
Abstract
The Jahn–Teller (JT) theorem constitutes one of the most fundamental concepts in chemistry. In transition-element chemistry, the 3d4 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 Na9Bi5Os3O24, 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.
Details
Original language | English |
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Pages (from-to) | 16500-16505 |
Number of pages | 6 |
Journal | Angewandte Chemie - International Edition |
Volume | 60 |
Issue number | 30 |
Publication status | Published - 19 Jul 2021 |
Peer-reviewed | Yes |
External IDs
PubMed | 33904630 |
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Keywords
ASJC Scopus subject areas
Keywords
- hydrothermal synthesis, Jahn–Teller compression, multinary osmate, spin–orbit coupling