Monoazadichalcogenasumanenes: Synthesis, Structures, and Ring Reconstruction via Atom Transfer under Acidic Conditions
Jihai Shang, Renjie Wang, Chengshan Yuan, Zitong Liu, Hao‐Li Zhang, Xiangfeng Shao
Abstract
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.