Photocyclization of 3DPA2FBN Yielding Core‐Edge Fused Donor–Acceptor Cyanoarene Photocatalysts

Donor–acceptor cyanoarenes are widely employed as photocatalysts, yet their photostability and degradation pathways remain critical areas of investigation. Herein we report that commercially available 3DPA2FBN, upon irradiation with blue light at room temperature, undergoes photocyclization events with extrusion of HF, generating structures in which the electron‐deficient cyanoarene core is fused to the diphenylamine‐derived electron‐rich periphery. A mono‐ and a bis‐cyclization product are obtained in regioselective fashion, along with a metastable precursor of the latter. These products were successfully isolated and fully characterized. Moreover, the two photostable photocyclized products were evaluated across various photocatalytic benchmarks. Our findings provide key insights into the chemical evolution of cyanoarene photocatalysts, demonstrating that degradation pathways can generate new, catalytically competent molecular species.