1. Azepine‐ or Azocine‐Embedded Hexabenzocoronene Derivatives as Nitrogen‐Doped Saddle or Saddle‐Helix Nanographenes
- Author
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Yi-Kang Zhang, Peng An, Ranran Li, Ming-Jun Xiao, Bin Ma, Run-Ying He, and Bin Zhang
- Subjects
chemistry.chemical_classification ,Materials science ,Alkene ,General Chemistry ,General Medicine ,Dihedral angle ,Fluorescence ,Catalysis ,chemistry.chemical_compound ,Crystallography ,Hexabenzocoronene ,chemistry ,Helix ,Azocine ,Azepine ,Antiaromaticity - Abstract
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 8π-heterocycles azepine and azocine in the NGs 1 and 2 exhibited obvious antiaromatic properties.
- Published
- 2021