Na9Bi5Os3O24: A Diamagnetic Oxide Featuring a Pronouncedly Jahn-Teller-Compressed Octahedral Coordination of Osmium(VI)
Autor(en): | Thakur, Gohil S. Reuter, Hans Ushakov, Alexey V. Gallo, Gianpiero Nuss, Juergen Dinnebier, Robert E. Streltsov, Sergey V. Khomskii, Daniel I. Jansen, Martin |
Stichwörter: | BONDS; Chemistry; Chemistry, Multidisciplinary; COMPLEXES; ENERGY; hydrothermal synthesis; Jahn-Teller compression; multinary osmate; spin-orbit coupling; TRANSITION | Erscheinungsdatum: | 2021 | Herausgeber: | WILEY-V C H VERLAG GMBH | Journal: | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | Volumen: | 60 | Ausgabe: | 30 | Startseite: | 16500 | Seitenende: | 16505 | Zusammenfassung: | 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 |
ISSN: | 14337851 | DOI: | 10.1002/anie.202103295 |
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