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Donor–Acceptor Polymers: A Conjugated Oligo( p ‐Phenylene Vinylene) Main Chain with Dangling Perylene Bisimides
Author(s) -
Neuteboom Edda E.,
van Hal Paul A.,
Janssen René A. J.
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400097
Subject(s) - photochemistry , photoinduced electron transfer , phenylene , acceptor , chromophore , perylene , electron acceptor , photoinduced charge separation , materials science , photoexcitation , quenching (fluorescence) , electron donor , ultrafast laser spectroscopy , chemistry , spectroscopy , electron transfer , polymer , fluorescence , excited state , organic chemistry , molecule , physics , catalysis , photocatalysis , quantum mechanics , artificial photosynthesis , nuclear physics , condensed matter physics , composite material
Two new donor–acceptor copolymers that consist of an enantiomerically pure oligo( p ‐phenylene vinylene) main chain with dangling perylene bisimides have been synthesized by using a Suzuki cross‐coupling polymerization. Absorption and circular dichroism spectroscopy revealed that the transition dipole moments of the donor in the main chain and the dangling acceptor moieties of the copolymers are coupled and in a helical orientation in solution, even at elevated temperatures. A strong fluorescence quenching of both chromophores indicates an efficient photoinduced charge transfer after photoexcitation of either donor or acceptor. The formation and recombination kinetics of the charge‐separated state were investigated in detail with femtosecond and near‐steady‐state photoinduced absorption spectroscopy. The charge‐separated state forms within 1 ps after excitation, and recombination occurs with a time constant of 45–60 ps, both in solution and in the solid state. These optical characteristics indicate a short distance and appreciable interaction between the electron‐rich donor chain and the dangling electron‐poor acceptor chromophores.