Hole-mediated photoredox catalysis: tris(p-substituted)biarylaminium radical cations as tunable, precomplexing and potent photooxidants

Shangze Wu, Jonas Žurauskas, Michał Domański, Patrick Hitzfeld, Valeria Butera, Daniel Scott, Julia Rehbein, Ajeet Kumar, Erling Thyrhaug, Jürgen Hauer, Joshua Barham

Research output: Contribution to journalArticlepeer-review

14 Citations (SciVal)

Abstract

As a combination of visible light photoredox catalysis and synthetic organic electrochemistry, 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. Herein we report a tunable class of electroactivated photoredox catalyst, tri(para-substituted)biarylamines, that become superoxidants in their photoexcited states even able to oxidize molecules beyond the solvent window limits of cyclic voltammetry (such as polyfluorobenzene and trifluorotoluene). Furthermore, we demonstrate that precomplexation not only permits the excited state photochemistry of tris(para-substituted)biarylaminium cations to overcome picosecond lifetime, but enables and rationalizes the surprising photochemistry of their higher-order doublet (Dn) excited states, unlocking extremely high oxidative potentials (up to a record-breaking ∼+4.4 V vs. SCE).
Original languageEnglish
Pages (from-to)1132-1142
JournalOrganic Chemistry Frontiers
Volume8
Issue number6
Early online date3 Mar 2021
DOIs
Publication statusPublished - 21 Mar 2021

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