Please use this identifier to cite or link to this item: http://hdl.handle.net/10995/111670
Title: Na9Bi5Os3O24: A Diamagnetic Oxide Featuring a Pronouncedly Jahn–Teller-Compressed Octahedral Coordination of Osmium(VI)
Authors: Thakur, G. S.
Reuter, H.
Ushakov, A. V.
Gallo, G.
Nuss, J.
Dinnebier, R. E.
Streltsov, S. V.
Khomskii, D. I.
Jansen, M.
Issue Date: 2021
Publisher: John Wiley and Sons Inc
Wiley
Citation: Na9Bi5Os3O24: A Diamagnetic Oxide Featuring a Pronouncedly Jahn–Teller-Compressed Octahedral Coordination of Osmium(VI) / G. S. Thakur, H. Reuter, A. V. Ushakov et al. // Angewandte Chemie - International Edition. — 2021. — Vol. 60. — Iss. 30. — P. 16500-16505.
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. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
Keywords: HYDROTHERMAL SYNTHESIS
JAHN–TELLER COMPRESSION
MULTINARY OSMATE
SPIN–ORBIT COUPLING
CHEMICAL ENGINEERING
CHEMICAL REACTIONS
CHEMISTRY
ELECTRONIC ENERGIES
ELECTRONIC SYSTEMS
FUNDAMENTAL CONCEPTS
OCTAHEDRAL COMPLEX
OCTAHEDRAL COORDINATION
STANDARD DISTANCE
STRUCTURAL CONSTRAINTS
TRANSITION ELEMENT
GROUND STATE
URI: http://hdl.handle.net/10995/111670
Access: info:eu-repo/semantics/openAccess
SCOPUS ID: 85108060325
PURE ID: 22820113
ISSN: 1433-7851
metadata.dc.description.sponsorship: G.S.T. thank the Cluster of Excellence (EXC 2147) funded by the Deutsche Forschungsgemeinschaft (DFG) for partial support. A.V.U. is grateful to the Quantum project (AAAA‐A18‐118020190095‐4). The work of D.Kh. was funded by the DFG (German Research Foundation)—Project number 277146847—CRC 1238. DFT+U calculations (S.V.S.) were supported by the Russian Science Foundation via RSF‐20‐62‐46047 project. Open access funding enabled and organized by Projekt DEAL. ct.qmat.
RSCF project card: 20-62-46047
Appears in Collections:Научные публикации, проиндексированные в SCOPUS и WoS CC

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