Metal‐Free, Blue‐Light‐Mediated Radical Trifluoromethylation of Small Organic Molecules

The development of a gentle and regioselective trifluoromethylation process is necessary due to the rise in organofluorine compounds, notably the inclusion of a –CF3 group in organic molecules for the pharmaceutical and materials sectors. This work presents novel examples of luminescent procarbenic purely organic photocatalysts (C1‐C3) that exhibit low‐negative irreversible reduction events (ERed = ‐0.86 V, ‐0.85 V and ‐0.68 V vs SCE for C1, C2 & C3, respectively) and strong ligand‐to‐ligand charge transfer absorption in the UV region (λabs ~ 280 nm). At room temperature (RT), both photocatalysts displayed deep‐blue 1LC emission in the 353‐373 nm region. These photocatalysts were found to be strong photo‐oxidants (EC(II)*/C(I) = 2.54 V, 2.65 V and 2.63 V vs SCE for C1, C2 and C3, respectively) and were employed as low‐cost, metal and additive‐free photocatalysts for the regioselective mono(trifluoromethylation) of polyaromatic hydrocarbons (PAHs) and small organic molecules in good yields (~ 42‐82%).