Na₉ Bi₅ Os₃ O₂₄ : A Diamagnetic Oxide Featuring a Pronouncedly Jahn-Teller-Compressed Octahedral Coordination of Osmium(VI).

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 Na₉ Bi₅ Os₃ O₂₄ , the octahedron around Os⁶⁺ (5d² ) 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.

SUBMITTER: Thakur GS 

PROVIDER: S-EPMC8361922 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature