The electron deficient ground state of the dications [E ~ -0.45 V (3a 2+ ), -0.36 V (4a 2+ ), -0.18 V (5a 2+ )] is by more than 500 mV positively shifted compared to monocationic Fukuzumi or Nicewicz catalysts (ca. -1.0 V, Figures and). This significant increase in the ground-state oxidation potential matches with the outlined motivation of accessing high oxidation potentials upon single photon excitation (Figure ). Due to its electron deficiency, we investigated the application of the dications as catalysts in strongly oxidizing photocatalysis. We selected oxidative arene azolation reactions as model transformations. Benzene was selected as the oxidative coupling partner and investigated in a Stern-Volmer experiment (Figure ). Indeed, we were delighted to observe that the fluorescence signal of dication 4a 2+ was linearly quenched upon addition of benzene (Figure ; inset) suggesting the possibility to oxidize benzene [Eox(benzene) ~ 2.5 V vs. SCE; vide infra]. We then investigated trapping of the benzene radical cation with 1H-pyrazole-4-carboxylate ( ) as a coupling partner under Kessil lamp irradiation (390 nm) employing catalytic amounts (5 mol%) of dication 4a 2+ and oxygen (1 atm) as stoichiometric oxidant at 25 °C in CH2Cl2. To our pleasure, the desired product ethyl 1-phenyl-1Hpyrazole-4-carboxylate 7 was obtained in 29% yield after 12 h (Table , entry 1, see the Supporting Information). Encouraged by this initial result, a further optimization of the reaction conditions was performed. Different light sources, solvents, oxidants, light intensity, catalyst loadings, additives, and low-temperature effects were screened (see Table -S8, Supporting Information). Gratifyingly, after these optimizations, the yield of the desired azolation product 7 increased to 93% in the presence of 5 mol% catalyst 4a 2+ 2SbF6 -, and 20 mol% LiClO4, in a solvent mixture trifluoroethanol (TFE):hexafluoroisopropanol (HFIP) (9:1) under 390 nm blue LED Kessil lamp irradiation for 12 h at 25 ℃ (Table , entry 1). [a] Reactions were performed using 0.4 mmol of pyrazole 6, benzene (8 mL), catalyst (5 mol%), LiClO4 (20 mol%), solvent mixture TFE:HFIP (9:1) and irradiated with two 390 nm Kessil lamps (40 W) for 12 h providing external water cooled chiller support to maintain the reaction temperature at 25 ℃. Yields determined by 1 H NMR using mesitylene as an internal standard. Increased reaction time to 24 h.