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

Abstract The development of a gentle and regioselective trifluoromethylation process is necessary due to the rise in organofluorine compounds, notably the inclusion of a −CF 3 group in organic molecules for the pharmaceutical and materials sectors. This work presents novel examples of luminescent procarbenic purely organic photocatalysts ( C1 – C3 ) that exhibited low‐negative irreversible reduction events (E Red =−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 (λ abs ~280 nm). At room temperature (RT), both photocatalysts displayed deep‐blue 1 LC emission in the 353–373 nm region. These photocatalysts were found to be strong photo‐oxidants (E C(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 %).