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Hole-Mediated PhotoRedox Catalysis: Tris(p-Substituted)biarylaminium Radical Cations as Tunable, Precomplexing and Potent Photooxidants

preprint
submitted on 25.10.2020, 15:53 and posted on 27.10.2020, 12:08 by Shangze Wu, Jonas Zurauskas, Michal Domanski, Patrick Hitzfeld, Valeria Butera, Daniel Scott, Julia Rehbein, Ajeet Kumar, Erling Thyrhaug, Jürgen Hauer, Joshua Barham

Electrochemically-mediated Photoredox Catalysis emerged as a powerful synthetic technique in recent years, overcoming fundamental limitations of electrochemistry and photoredox catalysis in the single electron transfer activation of small organic molecules. However, the mechanism of how photoexcited radical ion species with ultrashort (picosecond-order) lifetimes could ever undergo productive photochemistry has eluded synthetic chemists. We report tri(para-substituted)biarylamines as a tunable class of electroactivated photocatalysts that become superoxidants in their photoexcited states, even able to oxidize molecules (such as dichlorobenzene and trifluorotoluene) beyond the solvent window limits of cyclic voltammetry. Furthermore, we demonstrate that precomplexation not only permits the excited state photochemistry of tris(para-substituted)biarylaminium cations, but enables and rationalizes the surprising photochemistry of their higher-order doublet (Dn) excited states.

Funding

Sofja Kovalevskaja Award of the Alexander von Humboldt Foundation

History

Email Address of Submitting Author

Joshua-Philip.Barham@chemie.uni-regensburg.de

Institution

Universität Regensburg

Country

Germany

ORCID For Submitting Author

0000-0003-1675-9399

Declaration of Conflict of Interest

No conflict of interest.

Licence

Exports