Radical Ions of a π-Bowl Sumanene: Effects of Strained Structure on the Electronic Transitions.

Strained polyaromatic carbon molecules exhibit interesting properties owing to enhanced interactions between p orbitals of sp carbons; sumanene (SUM) is one of these bowl-shaped π-conjugated molecules (π-bowls). In the present study, the radical cation and radical anion of SUM were characterized by radiation chemical methods, that is, pulse radiolysis and γ-ray radiolysis. Absorption spectra of the SUM radical cation and radical anion in a wide spectral region ranging from the visible to near-IR were successfully obtained. Absorption spectra of the SUM radical cation and radical anion are similar in shape to those of the corresponding species of triphenylene (TP), which possesses a planar structure and the same π-electron system as SUM. However, the SUM radical anion showed lower peak shifts than the TP radical anion. Theoretical calculations revealed that the MOs responsible for the electronic transitions of the SUM radical anion are different from those of the TP radical anion, in contrast to the radical cations. These results demonstrate that the strains in the molecular geometries affect the electronic transitions of radical ions.