Persulfurated Coronene and Its Chalcogenide Analogues: Insight into Effects of Peripheral Substitution

The density functional theory (DFT) and time-dependent DFT methods have been used to investigate the persulfurated coronene (PSC) and its chalcogenide analogues (POC and PSeC), derived from the substitution of sulfur, oxygen, and selenium for all hydrogen atoms in coronene, respectively. The presence of peripheral S-S in PSC results in a σ-type lowest unoccupied molecular orbital and the dark low-lying states (S₁ ∼ S₁₅). The peripheral S-S bond is responsible for its electron capture, which maintains a planar configuration of the singly and doubly negative-charged PSC. POC is predicted to have the most stable saddle-shaped structure with the C═O group, and its bowl-shaped isomer with the O-O moiety is less stable by 279.2 kcal/mol energetically. PSeC has similar electronic and structural features with PSC, but its dimer is predicted to have much better hole mobility, compared to PSC. The present results indicate that the chalcogenide substitution at the periphery of the polycyclic aromatic hydrocarbons may remarkably change their electronic and spectroscopic properties as well as the carrier transport behavior of their molecular materials.