Abstract
We present a radical anion/dianion system, octabromo N-pentyl perylenediimide (PDI-Br8), that is both year-stable and air-stable, serving as an effective visible-light photocatalyst for the stereoselective synthesis of (E)-enenitriles. This reaction proceeds through a one-pot, three-component coupling of terminal alkynes, carbon tetrahalides, and acrylonitrile under ambient conditions. The radical anion of PDI-Br8, formed using tetrabutylammonium cyanide (TBAC) in acetonitrile under blue LED irradiation. Notably, the process achieves 100% atom economy with low E-factor, underscoring its high efficiency and sustainability.