Photoinduced Cascading Charge Transfer in Perylene Bisimide-Based Triads

We synthesize three perylene bisimide-based triads with donor-acceptor-acceptor (D∼A₁-A₂) architectures, in which the distance between D and A₁ is varied to study its influence on the excited state electron processes. Very different intramolecular charge transfer (D⁺∼A₁-A₂^-) lifetimes in dichloromethane (DCM) for these three triads are revealed by steady-state and transient spectroscopies. Free-energy changes of charge transfer (CT) are calculated based on the single-crystal X-ray diffraction data and electrochemical measurements. The results show that photoinduced cascading CT comprises two competing processes in DCM (CTs in D∼A1 units and in A1-A2 units) by pumping of the A1 unit, and then the long-distance CT state is formed. The charge recombination (CR) process is restrained effectively by the increased distance between the anion and cation. This research reveals the importance of multistep cascading CTs on tuning the CT lifetime in multichromophoric systems.