Issue 6, 2021

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

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).

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

Supplementary files

Article information

Article type
Research Article
Submitted
21 dec 2020
Accepted
17 feb 2021
First published
03 mar 2021
This article is Open Access
Creative Commons BY license

Org. Chem. Front., 2021,8, 1132-1142

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

S. Wu, J. Žurauskas, M. Domański, P. S. Hitzfeld, V. Butera, D. J. Scott, J. Rehbein, A. Kumar, E. Thyrhaug, J. Hauer and J. P. Barham, Org. Chem. Front., 2021, 8, 1132 DOI: 10.1039/D0QO01609H

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