Photophysical Properties of Homo- and Hetero-Aggregate Assemblies Made of N-Annulated Perylene Derivatives

We report the absorption spectra and photophysical properties of homo and hetero-aggregate assemblies of a strongly emissive N-annulated perylene dye (P) and of a dyad made of P and a methyl viologen derivative (P-MV), in ethanol-water solutions. In homo-aggregate assemblies of P, the pi-pi* fluorescence of the isolated chromophore is replaced by excimer emission at lower energy, with a lifetime of 900 ps, due to excimer formation from the initially prepared excitons. In homo-aggregate assemblies of P-MV, photoinduced charge separation, with formation of P+-MV- species, occurs in 3 ps with a charge recombination of 20 ps. In hetero-aggregate P/P-MV systems, the light energy absorbed by the P components delocalizes over various P subunits, and when a P-MV unit is reached, charge separation occurs; however, excimer emission is present for P/P-MV ratio larger than 3 : 1, indicating that delocalized excitons within the hetero-aggregate systems extend over a limited number of P chromophores.

Automated summary

This study reports the absorption spectra and photophysical properties of assemblies of a strongly emissive N-annulated perylene dye in ethanol-water solutions. It is found that excimer emission and charge separation occur in the homo-aggregate and hetero-aggregate assemblies, respectively. The extent of excimer emission is limited in the hetero-aggregate systems.