Electronic Effect‐Controlled Visible‐Light‐Driven Tetra‐Arylation of p ‐Benzoquinone Using a Phenalenyl–Pyrene Hybrid Photocatalyst

A phenalenyl–pyrene hybrid system is presented here as an effective photocatalyst for the direct C(sp 2 )─H arylation of p ‐benzoquinone under visible light. This process yields a range of biologically and optically relevant redox‐active tetra‐arylated‐ p ‐benzoquinones, utilizing aryl diazonium salts as radical sources. Additionally, the catalyst facilitates the conversion of tetra‐arylated‐ p ‐benzoquinones into dibenzofuran‐type molecules through intramolecular O─C coupling when aryl groups contain powerful inductive withdrawing groups. This study also provides mechanistic insights into the catalytic reaction and the structural characteristics of the synthesized tetra‐arylated products.