<p>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(<i>para</i>-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(<i>para</i>-substituted)biarylaminium
cations, but enables and rationalizes the surprising photochemistry of their <i>higher-order</i>
doublet (D<i><sub>n</sub></i>) excited states.</p>
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