Spectroscopic properties, excitation, and electron transfer in an anionic water-soluble poly(fluorene-alt-phenylene)-perylenediimide copolymer.

The Journal of Physical Chemistry. B
Ana T MarquesAndrew P Monkman

Abstract

An anionic fluorene-phenylene poly{1,4-phenylene-[9,9-bis(4-phenoxy-butylsulfonate)]fluorene-2,7-diyl}-based copolymer containing on-chain perylenediimine (PDI) chromophoric units, PBS-PFP-PDI, was synthesized and its photophysical properties studied as aggregates and isolated chains in water and dioxane/water (1:1) solution. UV-vis and emission spectroscopy measurements, time-correlated single photon counting, and wide field imaging have been employed to investigate the excited-state behavior of the PBS-PFP-PDI copolymer, including the effect of environment on the energy and electron transfer to the on-chain PDI chromophore. Although the Förster overlap integral is favorable, no evidence is found for intramolecular singlet excitation energy transfer in isolated copolymer chains in solution. Fluorescence is suggested to involve an interchain process, thus revealing that isolated copolymer chains in solution do not undergo efficient intramolecular energy transfer. However, quenching of the PBS-PFP excited state by PDI is observed in aqueous media and ultrafast pump-probe studies in water or dioxane-water solutions show that electron transfer occurs from the phenylene-fluorene units to the PDI. The extent of electron transfer inc...Continue Reading

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