The properties of the excited perylenediimide dianion (PDI2-∗) and its intramolecular electron transfer (ET) behavior were examined using femtosecond laser flash photolysis on PDI2- and PDI2--acceptor (A) dyads. Upon laser excitation, the dianion of PDI first generated a singlet (S1) state, followed by a triplet (T1) state. In all of the dyads, rate constants of the intramolecular ET from PDI2-∗ (S1) varied with the driving forces. Comparison of the PDI2-∗-A and PDI•-∗-A dyad systems revealed higher rate constants for the ET from PDI2-∗ than from PDI•-∗, which can be attributed to the difference in electronic coupling for the ET. These findings elucidate the previously unexplored photoinduced ET characteristics of PDI2-, thereby advancing the groundwork for photochemical studies of excited multi-ions and their applications in related materials.
Read full abstract