Direct Investigation of Excited C60 Dianion and Its Intramolecular Electron Transfer Behaviors.

ABSTRACT

For the first time, the dynamics of excited fullerene dianions and associated intramolecular electron transfer (ET) were directly investigated by using femtosecond pump-probe laser flash photolysis on selectively reduced C60, pyrrolidino[60]fullerene (C60H), and dyads including C60-naphthalenediimide (NDI) and C60-pyromellitimide (PI). Upon near-infrared laser excitation, the excited dianion of C60 or C60H displayed two states with lifetimes of less than one and several tens of ps, attributed to prompt internal conversion from the theoretically predicted Sn state. Furthermore, the ET processes from the excited C602- in dyad molecules, including C602--NDI•- and C602--PI•-, were confirmed with varied ET rate constants due to the difference in the driving force for ET. The current findings provide a clear description of the hitherto uncharted excited-state and photoinduced ET characteristics of fullerene dianions, paving the way for photochemical studies of excited multi-ions (excited multi-polarons) and their application in organic semiconducting materials.