Electrochemical Properties and Excited-State Dynamics of Azaperylene Derivatives

A series of azaperylene derivatives such as monoazaperylene (MAPery), 1,6-diazaperylene (1,6-DiAPery), 1,7-diazaperylene (1,7-DiAPery), 1,12-diazaperylene (1,12-DiAPery), triazaperylene (TriAPery), and tetraazaperylene (TetAPery) was synthesized by changing the position and number of nitrogen atoms at the bay region of a perylene skeleton in 1, 6, 7, and 12 positions. The density functional theory (DFT) calculations and electrochemical measurements suggested that the energies of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) states significantly become stabilized with increasing the number of nitrogen atoms, whereas the estimated HOMO-LUMO gaps approximately remain constant. This result is in good agreement with the absorption and fluorescence spectral measurements. Additionally, these steady-state spectroscopic measurements demonstrate the broadened spectra as compared to pristine perylene (Pery). In photophysical measurements, the fluorescence quantum yields (Φ_FL) significantly decreased as the number of nitrogen atoms increased, whereas much enhanced quantum yields and rate constants of internal conversion (Φ_IC and k_IC) were observed. Especially, the increased k_IC values of TriAPery (k_IC: ∼10⁸ s^-1) and TetAPery (k_IC: ∼10⁹ s^-1) are much larger than those of diazaperylene and monoazaperylene derivatives (k_IC: ∼10⁷ s^-1). These photophysical trends were successfully explained by time-dependent DFT (TD-DFT) calculations. Finally, the characteristic protonated and deprotonated processes of nitrogen atoms in azaperylenes under acidic conditions were monitored utilizing absorption and fluorescence measurements. The binding constants demonstrate that the nitrogen atoms at 1 and 12 positions of a perylene skeleton are essential for the increased values.