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

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.


Sofja Kovalevskaja Award of the Alexander von Humboldt Foundation


Email Address of Submitting Author


Universität Regensburg



ORCID For Submitting Author


Declaration of Conflict of Interest

No conflict of interest.