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A Stable Crystalline Triarylphosphine Oxide Radical Anion

Tobias A. Schaub

Chair of Organic Chemistry I, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Henkestrasse 42, 91054 Erlangen, Germany

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Eva M. Zolnhofer,

Eva M. Zolnhofer

Chair of General and Inorganic Chemistry, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany

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Dominik P. Halter,

Dominik P. Halter

Chair of General and Inorganic Chemistry, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany

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Dr. Tatyana E. Shubina,

Dr. Tatyana E. Shubina

Computer Chemistry Center (CCC), University of Erlangen-Nürnberg, Nägelsbachstrasse 25, 91052 Erlangen, Germany

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Dr. Frank Hampel,

Dr. Frank Hampel

Chair of Organic Chemistry I, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Henkestrasse 42, 91054 Erlangen, Germany

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Prof. Dr. Karsten Meyer,

Prof. Dr. Karsten Meyer

Chair of General and Inorganic Chemistry, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany

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Dr. Milan Kivala,

Corresponding Author

Dr. Milan Kivala

[email protected]

Chair of Organic Chemistry I, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Henkestrasse 42, 91054 Erlangen, Germany

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Tobias A. Schaub,

Tobias A. Schaub

Chair of Organic Chemistry I, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Henkestrasse 42, 91054 Erlangen, Germany

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Eva M. Zolnhofer,

Eva M. Zolnhofer

Chair of General and Inorganic Chemistry, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany

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Dominik P. Halter,

Dominik P. Halter

Chair of General and Inorganic Chemistry, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany

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Dr. Tatyana E. Shubina,

Dr. Tatyana E. Shubina

Computer Chemistry Center (CCC), University of Erlangen-Nürnberg, Nägelsbachstrasse 25, 91052 Erlangen, Germany

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Dr. Frank Hampel,

Dr. Frank Hampel

Chair of Organic Chemistry I, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Henkestrasse 42, 91054 Erlangen, Germany

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Prof. Dr. Karsten Meyer,

Prof. Dr. Karsten Meyer

Chair of General and Inorganic Chemistry, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany

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Dr. Milan Kivala,

Corresponding Author

Dr. Milan Kivala

[email protected]

Chair of Organic Chemistry I, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Henkestrasse 42, 91054 Erlangen, Germany

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First published: 27 September 2016

https://doi.org/10.1002/anie.201605963

Citations: 39

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Graphical Abstract

The spin within: A carefully designed triarylphosphine oxide scaffold with sterically demanding spirofluorenyl moieties undergoes chemical one-electron reduction at its phosphoryl moiety. The unique stability of the formed radical anion enables the isolation and X-ray crystallographic characterization of this hitherto elusive species.

Abstract

Triarylphosphine oxides (Ar₃P=O) are being intensely studied as electron-accepting (n-type) materials. Despite the widespread application of these compounds as electron conductors, experimental data regarding the structural and electronic properties of their negatively charged states remain scarce owing to their propensity for follow-up chemistry. Herein, a carefully designed triarylphosphine oxide scaffold is disclosed that comprises sterically demanding spirofluorenyl moieties to shield the central phosphoryl (P=O) moiety. This compound undergoes chemical one-electron reduction to afford an exceptionally stable radical anion, which was isolated and characterized by X-ray crystallography for the very first time. The experimental data, corroborated by computational studies, shall allow for the construction of phosphine oxide materials with enhanced stability.

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Volume55, Issue43

October 17, 2016

Pages 13597-13601

A Stable Crystalline Triarylphosphine Oxide Radical Anion

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A Stable Crystalline Triarylphosphine Oxide Radical Anion

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