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.
%0 Journal Article
%1 https://doi.org/10.1002/anie.202103295
%A Thakur, Gohil S.
%A Reuter, Hans
%A Ushakov, Alexey V.
%A Gallo, Gianpiero
%A Nuss, Jürgen
%A Dinnebier, Robert E.
%A Streltsov, Sergey V.
%A Khomskii, Daniel I.
%A Jansen, Martin
%D 2021
%J Angew. Chem. Int. Ed.
%K a
%N 30
%P 16500-16505
%R https://doi.org/10.1002/anie.202103295
%T Na$_9$Bi$_5$Os$_3$O$_24$: a diamagnetic oxide featuring a pronouncedly Jahn–Teller-compressed octahedral coordination of osmium(VI)
%U https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202103295
%V 60
%X 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.
@article{https://doi.org/10.1002/anie.202103295,
abstract = {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.},
added-at = {2023-11-16T13:02:35.000+0100},
author = {Thakur, Gohil S. and Reuter, Hans and Ushakov, Alexey V. and Gallo, Gianpiero and Nuss, Jürgen and Dinnebier, Robert E. and Streltsov, Sergey V. and Khomskii, Daniel I. and Jansen, Martin},
biburl = {https://www.bibsonomy.org/bibtex/203286c52bf459e4e830c9d3826c42318/ctqmat},
day = 27,
doi = {https://doi.org/10.1002/anie.202103295},
eprint = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.202103295},
interhash = {f2ec60b27175fde08d8b5f45e9689daf},
intrahash = {03286c52bf459e4e830c9d3826c42318},
journal = {Angew. Chem. Int. Ed.},
keywords = {a},
month = {04},
number = 30,
pages = {16500-16505},
timestamp = {2023-11-24T11:44:45.000+0100},
title = {Na$_{\mathbf{9}}$Bi$_{\mathbf{5}}$Os$_{\mathbf{3}}$O$_{\mathbf{24}}$: a diamagnetic oxide featuring a pronouncedly Jahn–Teller-compressed octahedral coordination of osmium(VI)},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202103295},
volume = 60,
year = 2021
}