Extension of Non-alternant Nanographenes Containing Nitrogen-Doped Stone-Thrower-Wales Defects

Non-alternant topologies have attracted considerable attention due to their unique physiochemical characteristics in recent years. Here, three novel topological nanographenes molecular models of nitrogen-doped Stone-Thrower-Wales (S-T-W) defects were achieved through intramolecular direct arylation. Their chemical structures were unambiguously elucidated by single-crystal analysis. Among them, threefold intramolecular direct arylation compound (C₄₂ H₂₁ N) is the largest nanographene bearing a N-doped non-alternant topology to date, in which the non-benzenoid rings account for 83 % of the total molecular skeleton. The absorption maxima of this compound was located in the near-infrared region with a long tail up to 900 nm, which was much longer than those reported for similarly sized N-doped nanographene with six-membered rings (C₄₀ H₁₅ N). In addition, the electronic energy gaps of these series compounds clearly decreased with the introduction of non-alternant topologies (from 2.27 eV to 1.50 eV). It is noteworthy that C₄₂ H₂₁ N possesses such a low energy gap (E_g ^opt =1.40 eV; E_g ^cv =1.50 eV), yet is highly stable under ambient conditions. Our work reported herein demonstrates that the non-alternant topology could significantly influence the electronic configurations of nanocarbons, where the introduction of a non-alternanting topology may be an effective way to narrow the energy gap without extending the molecular π-conjugation.