title: Electron transfer at the single-molecule level in a triphenylamine-perylene imide molecule.
abstract: Photoinduced electron transfer (ET) processes in a donor-acceptor system based on triphenylamine and perylene imide have been studied at the single-molecule (SM) and ensemble levels. The system exists as two isomers, one of which undergoes forward and reverse ET in toluene with decay constants of 3.0 and 2.2x10(9) s(-1), respectively, resulting in the dual emission of quenched and delayed fluorescence while the other isomer remains ET-inactive. The fluorescence of both isomers is heavily quenched in the more polar solvent, diethyl ether, by ET. A broad range of ET dynamics is seen at the SM level in polystryene with the two isomers nonresolvable indicating that the local nanoenvironment of the SMs varies considerably throughout the polymer matrix. Both the electronic coupling and the driving force for ET are shown to influence the ET dynamics. Many fluorescence trajectories of SMs show long periods (tens of milliseconds to seconds) where the count rate is attenuated either partly (a "dim" state) or to the background level (an "off-time"). During these periods, the reduction or interruption of emission is attributed to cycles of rapid charge separation followed by charge recombination to the ground state reducing the fluorescence quantum yield of the SM.
authors.affiliation: Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, 3001 Heverlee, Belgium.
authors.forename: Toby D M
authors.initials: TD
authors.lastname: Bell
authors.forename: Alina
authors.initials: A
authors.lastname: Stefan
authors.forename: Sadahiro
authors.initials: S
authors.lastname: Masuo
authors.forename: Tom
authors.initials: T
authors.lastname: Vosch
authors.forename: Marc
authors.initials: M
authors.lastname: Lor
authors.forename: Mircea
authors.initials: M
authors.lastname: Cotlet
authors.forename: Johan
authors.initials: J
authors.lastname: Hofkens
authors.forename: Stefan
authors.initials: S
authors.lastname: Bernhardt
authors.forename: Klaus
authors.initials: K
authors.lastname: Müllen
authors.forename: Mark
authors.initials: M
authors.lastname: van der Auweraer
authors.forename: Jan W
authors.initials: JW
authors.lastname: Verhoeven
authors.forename: Frans C
authors.initials: FC
authors.lastname: De Schryver