Deprotonation of isoazatruxene enables photocatalytic arylation and phosphorylation of (hetero)aryl halides

generates the N-centered isoazatruxene anionic species (ITN3-), which exhibits enhanced visible-light absorption and potent reducing ability. Under the photocatalysis of ITN3-, the dehalogenative arylation and phosphorylation of aryl halides can be efficiently achieved, enabling the rapid assembly of pyrrole-containing biaryls and aryl phosphonates. The synthetic utility is further demonstrated by late-stage modification of complex molecules and multi-phosphorylation. Mechanistic studies confirm that the deprotonation of isoazatruxene results in enhanced visible-light absorption and improved photophysical properties.