Azepine- or Azocine-Embedded Hexabenzocoronene Derivatives as Nitrogen-Doped Saddle or Saddle-Helix Nanographenes

Two novel nitrogen-doped, hexa-peri-hexabenzocoronene (HBC)-based nanographenes (NGs) 1 and 2 bearing an azepine and an azocine at the fjord region, respectively, were synthesized and characterized. Notably, structure 1 was synthesized by Diels-Alder reaction of cyclic alkene and tetrachlorothiophene-S,S-dioxide, followed by Suzuki-Miyaura cross-coupling and Scholl-type reactions, which represents a modified strategy to construct NGs. The azo-heptagon-embedded NG 1 leads to a saddle shape, and the azo-octagon-embedded NG 2 exhibits a distorted saddle-helix conformation with the largest torsion angle recorded so far in [5]helicenes. As a result, the different structural topographies for NGs 1 and 2 lead to significant changes in the optical properties including UV absorption and fluorescent emission. Additionally, the 8 pi-heterocycles azepine and azocine in the NGs 1 and 2 exhibited obvious antiaromatic properties.

Automated summary

Two novel nitrogen-doped nanographenes were synthesized with distinct structures and optical properties. These nanographenes exhibited unique molecular conformations and antiaromatic properties.