%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 }