JOURNAL ARTICLE

Alternating oligo(p-phenylene vinylene)—perylene bisimide copolymers: synthesis, photophysics, and photovoltaic properties of a new class of donor—acceptor materials

Edda E Neuteboom, Stefan C J Meskers, Paul A van Hal, Jeroen K J van Duren, E W Meijer, René A J Janssen, Hélène Dupin, Geoffrey Pourtois, Jérôme Cornil, Roberto Lazzaroni, Jean-Luc Brédas, David Beljonne
Journal of the American Chemical Society 2003 July 16, 125 (28): 8625-38
12848570
A Suzuki polycondensation reaction has been used to synthesize two copolymers consisting of alternating oligo(p-phenylene vinylene) (OPV) donor and perylene bisimide (PERY) acceptor chromophores. The copolymers differ by the length of the saturated spacer that connects the OPV and PERY units. Photoinduced singlet energy transfer and photoinduced charge separation in these polychromophores have been studied in solution and in the solid state via photoluminescence and femtosecond pump-probe spectroscopy. In both polymers a photoinduced electron transfer occurs within a few picoseconds after excitation of the OPV or the PERY chromophore. The electron transfer from OPV excited state competes with a singlet energy transfer state to the PERY chromophore. The differences in rate constants for the electron- and energy-transfer processes are discussed on the basis of correlated quantum-chemical calculations and in terms of conformational preferences and folding of the two polymers. In solution, the lifetime of the charge-separated state is longer than in the films where geminate recombination is much faster. However, in the films some charges are able to escape from geminate recombination and diffuse away and can be collected at the electrodes when the polymers are incorporated in a photovoltaic device.

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