Unraveling Excited-State Dynamics in a Polyfluorene-Perylenediimide Copolymer

Eduard Fron, Ania Deres, Susana Rocha, Gang Zhou, Klaus Müllen, Frans C. De Schryver, Michel Sliwa, Hiroshi Uji-i, Johan Hofkens, Tom Vosch (see publication in Journal )


Insight into the exciton dynamics occurring in a polyfluorene-perylenediimide (PF-PDI) copolymer with a reaction mixture ratio of 100 fluorene units to 1 N,N′-bis(phenyl)-1,6,7,12-tetra(p-tert-octylphenoxy)-perylene-3,4,9,10-tetracarboxylic acid diimide (PDI) is presented here. Time-correlated single photon counting and femtosecond transient absorption spectroscopy measurements on the PF-PDI copolymer have been employed to investigate the excited-state properties of the polyfluorene subunit where the exciton is localized (PF) and the incorporated PDI chromophore. The experimental results were compared with those obtained from a polyfluorene polymer (model PF) and a N,N′-bis(2,6-diisopropylphenyl)-1,6,7,12-tetra(p-tert-octylphenoxy)-perylene-3,4,9,10-tetracarboxylic acid diimide (model PDI) which were used as reference compounds. Because of the high polydispersity of the PF-PDI copolymer, there is a polymer fraction present that contains no PDI chromophores (polyfluorene polymer fraction (PF polymer fraction)), and wide-field imaging of single polymers chains of the synthesized PF-PDI copolymer was used to estimate this PF polymer fraction. Following the primary excitation of the PF in the PF-PDI copolymer, energy hopping between PF’s can occur. A fraction of the energy of the absorbed photons will be transferred to a PDI chromophore via energy transfer from a PF. In a polar solvent, a charge transfer state having the S1 of the PDI moiety as a precursor state is found to form with high efficiency on a nanosecond time scale. The data suggest that a fraction of the absorbed energy is directed, transferred, and used in charge separation, providing a clear view of a multistep mechanism of exciton dissociation into charges.