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

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Gohil S. Thakur - , Chair of Inorganic Chemistry II, Max Planck Institute for Chemical Physics of Solids (Author)
  • Hans Reuter - , University Osnabruck (Author)
  • Alexey V. Ushakov - , RAS - Mikheev Institute of Metal Physics, Ural Branch (Author)
  • Gianpiero Gallo - , Max Planck Institute for Solid State Research (Author)
  • Jürgen Nuss - , Max Planck Institute for Solid State Research (Author)
  • Robert E. Dinnebier - , Max Planck Institute for Solid State Research (Author)
  • Sergey V. Streltsov - , RAS - Mikheev Institute of Metal Physics, Ural Branch, Ural Federal University (Author)
  • Daniel I. Khomskii - , University of Cologne (Author)
  • Martin Jansen - , Max Planck Institute for Solid State Research (Author)

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 languageEnglish
Pages (from-to)16500-16505
Number of pages6
JournalAngewandte Chemie - International Edition
Volume60
Issue number30
Publication statusPublished - 19 Jul 2021
Peer-reviewedYes

External IDs

PubMed 33904630

Keywords

ASJC Scopus subject areas

Keywords

  • hydrothermal synthesis, Jahn–Teller compression, multinary osmate, spin–orbit coupling