It was envisaged that Lewis acid activation could be leveraged to lower the reduction potential of previously unreactive substrates and facilitate the desired photocleavage of the N-O bond. LiBF4 (LA) was chosen as an exogenous Lewis acid and its competence was initially tested in CV experiments. As anticipated, the reduction potential of the phenyl, p-bromo and p-methyl substrate shifted to higher reduction potentials (Figure , part 3 for p-methyl, p-Br and phenyl (B-C) see ESI). Unfortunately, although the shifted reduction potentials are lower than that of anthracene, the desired product was only observed in trace amounts. Consequently, alternative reducing photocatalysts were considered. 4CzIPN has been demonstrated to be an attractive alternative to common transition metal-based photocatalysts due to its well-defined photophysical properties and a broad redox window. Moreover, a seminal report by Wu and co-workers demonstrated that the redox window of 4CzIPN can be further expanded by a ConPET mechanism. The radical anion formed upon excitation and subsequent reduction with an electron donor is long-lived and can undergo re-excitation to form a highly reducing species. We envisaged that this process utilizing a highly reductive excited catalyst radical anion could provide a solution to the obstinate challenge presented by this N-O bond cleavage event (Figure , part 5). These CV experiments support the experimental data observed above (Figure , part 1): electron rich substrates (A-D), which proved to be unreactive under the reaction conditions, have a higher reduction potential than the anthracene radical anion. Plotting the measured redox potentials against the Hammett σ p parameters lends further support to this hypothesis (R 2 = 0.98) (Figure , part 2).