Previous reports motivated us to screen the optimization in the presence of fluorinated solvents which offer higher stability of the involved radical cations. Only a slight reduction in yield (84%) was observed when the reaction was carried out without LiClO4 (Table , entry 2). Note, without any additives, Nicewicz and N-phenylphenothiazine catalysts failed to activate arenes with a satisfactory yield. To confirm if air was required for the photocatalytic reaction, the reaction was carried out under an argon atmosphere. As expected, the desired product 7 did form only in traces (2%) in the absence of air ( identified 4a 2+ to be superior compared to the other dicationic hybrids 3a 2+ and 5a although the catalysts also afforded high yields especially upon prolonged irradiation times for 24 h (Table and Figure ). Next, under identical conditions, the influence of the N-substitution was investigated by using catalysts 4a 2+ (N-Me) and 4b 2+ (N-Ph). We reasoned that N-Ph substitution should be superior in its performance since the N-Me group could be prone to dealkylation as potential catalyst decomposition pathway. Gratifyingly, both catalysts performed similarly well 93% (4a 2+ ) and 91% (4b 2+ ), most likely since with 5 mol% catalyst loading the catalyst decomposition is not yet relevant. In fact, we investigated lowering both catalyst loadings of 4a 2+