[OsF6]x−: Molecular Models for Spin-Orbit Entangled Phenomena

Kasper S. Pedersen; Daniel N. Woodruff; Saurabh Kumar Singh; Alain Tressaud; Etienne Durand; Mihail Atanasov; Panagiota Perlepe; Katharina Ollefs; Fabrice Wilhelm; Corine Mathonière; Frank Neese; Andrei Rogalev; Jesper Bendix; Rodolphe Clérac

doi:10.1002/chem.201702894

[OsF₆]^x−: Molecular Models for Spin-Orbit Entangled Phenomena

Kasper S. Pedersen, Daniel N. Woodruff, Saurabh Kumar Singh, Alain Tressaud, Etienne Durand, Mihail Atanasov, Panagiota Perlepe, Katharina Ollefs, Fabrice Wilhelm, Corine Mathonière, Frank Neese, Andrei Rogalev, Jesper Bendix, Rodolphe Clérac

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

Heavy 5d elements, like osmium, feature strong spin-orbit interactions which are at the origin of exotic physical behaviors. Revealing the full potential of, for example, novel osmium oxide materials (“osmates”) is however contingent upon a detailed understanding of the local single-ion properties. Herein, two molecular osmate analogues, [OsF₆]²⁻ and [OsF₆]⁻, are reported as model systems for Os⁴⁺ and Os⁵⁺ centers found in oxides. Using X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) techniques, combined with state-of-the-art ab initio calculations, their ground state was elucidated; mirroring the osmium electronic structure in osmates. The realization of such molecular model systems provides a unique chemical playground to engineer materials exhibiting spin-orbit entangled phenomena.

Original language	English (US)
Pages (from-to)	11244-11248
Number of pages	5
Journal	Chemistry - A European Journal
Volume	23
Issue number	47
DOIs	https://doi.org/10.1002/chem.201702894
State	Published - Aug 22 2017
Externally published	Yes

Bibliographical note

Funding Information:
The authors thank E. Lebraud, S. Exiga, M. Rouzières, and P. Voisin for technical and experimental assistance. The X-ray spectroscopy experiments were performed at the European Synchrotron Radiation Facility (ESRF, Grenoble, France). K.S.P. and R.C. thank the Danish Research Council for Independent Research for a DFF-Sapere Aude Research Talent grant (4090-00201), the University of Bordeaux, the Région Nouvelle Aquitaine, the CNRS and the GdR MCM-2: Magnétisme et Commutation Moléculaires.

Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

5d elements
X-ray spectroscopy
ab initio calculations
magnetism
osmium
spin-orbit interaction

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Cite this

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title = "[OsF6]x−: Molecular Models for Spin-Orbit Entangled Phenomena",

abstract = "Heavy 5d elements, like osmium, feature strong spin-orbit interactions which are at the origin of exotic physical behaviors. Revealing the full potential of, for example, novel osmium oxide materials (“osmates”) is however contingent upon a detailed understanding of the local single-ion properties. Herein, two molecular osmate analogues, [OsF6]2− and [OsF6]−, are reported as model systems for Os4+ and Os5+ centers found in oxides. Using X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) techniques, combined with state-of-the-art ab initio calculations, their ground state was elucidated; mirroring the osmium electronic structure in osmates. The realization of such molecular model systems provides a unique chemical playground to engineer materials exhibiting spin-orbit entangled phenomena.",

keywords = "5d elements, X-ray spectroscopy, ab initio calculations, magnetism, osmium, spin-orbit interaction",

author = "Pedersen, {Kasper S.} and Woodruff, {Daniel N.} and Singh, {Saurabh Kumar} and Alain Tressaud and Etienne Durand and Mihail Atanasov and Panagiota Perlepe and Katharina Ollefs and Fabrice Wilhelm and Corine Mathoni{\`e}re and Frank Neese and Andrei Rogalev and Jesper Bendix and Rodolphe Cl{\'e}rac",

note = "Funding Information: The authors thank E. Lebraud, S. Exiga, M. Rouzi{\`e}res, and P. Voisin for technical and experimental assistance. The X-ray spectroscopy experiments were performed at the European Synchrotron Radiation Facility (ESRF, Grenoble, France). K.S.P. and R.C. thank the Danish Research Council for Independent Research for a DFF-Sapere Aude Research Talent grant (4090-00201), the University of Bordeaux, the R{\'e}gion Nouvelle Aquitaine, the CNRS and the GdR MCM-2: Magn{\'e}tisme et Commutation Mol{\'e}culaires. Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Pedersen, Kasper S.

AU - Woodruff, Daniel N.

AU - Singh, Saurabh Kumar

AU - Tressaud, Alain

AU - Durand, Etienne

AU - Atanasov, Mihail

AU - Perlepe, Panagiota

AU - Ollefs, Katharina

AU - Wilhelm, Fabrice

AU - Mathonière, Corine

AU - Neese, Frank

AU - Rogalev, Andrei

AU - Bendix, Jesper

AU - Clérac, Rodolphe

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