Carbon-bridged oligo(phenylenevinylene)s: stable π-systems with high responsiveness to doping and excitation

The high responsiveness of π-conjugated materials to external stimuli, such as electrons and photons, accounts for both their utility in optoelectronic applications and their chemical instability. Extensive studies on heteroatom-stabilized π-conjugated systems notwithstanding, it is still difficult to combine high performance and stability. We report here that carbon-bridged oligo(p-phenylenevinylene)s (COPV-n) are not only more responsive to doping and photoexcitation but also more stable than the conventional p-phenylenevinylenes and poly(3-hexylthiophene), surviving photolysis very well in air, suggesting that they could serve as building blocks for optoelectronic applications. Activation of the ground state by installation of bond angle strain toward the doped or photoexcited state and the flat, rigid, and hindered structure endows COPVs with stimuli-responsiveness and stability without recourse to heteroatoms. For example, COPV-6 can be doped with an extremely small reorganization energy and form a bipolaron delocalized over the entire π-conjugated system. Applications to bulk and molecular optoelectronic devices are foreseen.