Monoazadichalcogenasumanenes: Synthesis, Structures, and Ring Reconstruction via Atom Transfer under Acidic Conditions.

Buckybowls have unique properties that can be tailored by embedding main‐group elements into their π‐scaffolds. Herein, a synthetic approach is developed for producing monoazadichalcogenasumanenes (4 a/4 b, 6 a/6 b, 7 a/7 b) derived from sumanene by replacing its three benzylic carbons with one nitrogen and two chalcogen atoms (S for 4 a/4 b, Se for 6 a/6 b, Te for 7 a/7 b). Monoazadichalcogenasumanenes are deeper π‐bowls than trichalcogensumanenes as the C−N bond is much shorter than C−X (X=S, Se, Te). The bowl‐depth of 4 b (0.95 Å) is greater than that of corannulene (0.85 Å). The nitrogen atom donates electron density to the entire π‐system that makes monoazadichalcogenasumanenes electron‐rich. They undergo ring reconstruction of chalcogenophene ring via transferring a chalcogen atom from one molecule to another under acidic conditions. The nitrogen and chalcogen atoms play crucial role on this reaction. [ABSTRACT FROM AUTHOR]