Relaxation dynamics of higher excited states of perylene-substituted perylene bisimide derivatives

Stepwise two-photon absorption processes have received considerable attention, especially in photocatalysis, due to their relatively lower power threshold, characteristic spatial selectivity, amplification of chemical reactions, and so on. Meanwhile, studies on the relaxation dynamics of higher excited states in condensed systems have been limited for several molecular systems due to the short-lived nature of these states. In this study, we synthesized perylene-substituted perylene bisimide (PBI) and its derivate as model compounds and investigated their excited-state dynamics, including higher excited states, using pump–repump–probe spectroscopy. We revealed that these molecules form charge-transfer (CT) states instantaneously after the excitation, regardless of whether it is the perylene moiety or the PBI moiety that is excited. The lifetime of the CT state was shorter when the distance between the donor (perylene) and the acceptor (PBI) was shorter. Moreover, we also revealed that a higher-lying CT state generated by the stepwise excitation of the CT state using a 740-nm pulse induced Stark effect to the neighboring perylene moiety. The Stark effect not only gives more detailed information about the CT state, but also presents the possibility of new photofunctions, such as instantaneous modulation of the electronic state to achieve optimal electronic properties. These insights contribute to understanding advanced photochemical reactions and would be important for exploring photocatalytic reactions involving higher excited states.