The azepine- and oxepine-embedded polycyclic aromatic hydrocarbons (PAH) 1-3, as the hexa-peri-hexabenzocoronene (HBC)-based nanographenes (NG) were designed and synthesized by Diels-Alder reaction of cyclic alkene with tetrachlorothiophene-S,S-dioxide, followed by Suzuki-Miyaura cross-coupling and Scholl-type cyclodehydrogenation. Due to the strained seven-membered ring and the inherent structural pattern, heteroatom-doped NGs 1-3 show Cs symmetrical, double saddle-helix hybrid conformation, which represents a new shape for HBC based nanographenes. The calculation studies reveal the low aromaticity of the 8π heterocycles themselves and the heterocycles also decrease the electron delocalization of benzenes surrounding them. Dynamics-based calculation suggests the Cs symmetry would maintain druing the saddle-inversion process. Meanwhile, we show property perturbation by doping with different heteroatoms.
Keywords: aromaticity; heteroatom-doped structure; nanographene; polycyclic aromatic hydrocarbon; saddle-helix.
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