Unmasking Electronic Energy Transfer of Conjugated Polymers by Suppression of O 2 Quenching

Abstract

The photochemistry of poly[2-methoxy, 5-(2′-ethyl-hexyloxy)- p -phenylene-vinylene] (MEH-PPV) has been found to be highly dependent on the presence of O ₂ , which increases singlet exciton quenching dramatically. Spectroscopy on isolated single molecules of MEH-PPV in polycarbonate films that exclude O ₂ reveals two distinct polymer conformations with fluorescence maxima near 555 and 580 nanometers wavelength, respectively. Time-resolved single-molecule data demonstrate that the 580-nanometer conformation exhibits a “landscape” for intramolecular electronic energy relaxation with a “funnel” that contains a 580-nanometer singlet exciton trap at the bottom. The exciton traps can be converted to exciton quenchers by reaction with O ₂ . Conformationally induced, directed-energy transfer is arguably a critical dynamical process that is responsible for many of the distinctive photophysical properties of conjugated polymers.