Abstract

Synthetic polymers incorporating appropriate chromophores can act as light harvesting antennae for artificial photosynthetic systems. The photophysical processes occurring in a polymer based on phenylene vinylene have been investigated at the single chain level and in bulk solution to study energy transfer processes. Most single chains of an alternating copolymer of 2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene and 1,4-phenylene vinylene (alt-co-MEH-PPV) dispersed in a transparent polymer matrix act as single chromophore emitters demonstrating that energy transfer is an efficient process in these polymers. However for individual polymer chains there are fluctuations in emission intensity ('blinking') and shifts in emission spectra, decay lifetimes and emission dipole orientation occurring on a time-scale of tens of seconds. Fluorescence blinking also occurs on a sub-millisecond time-scale and follows exponential kinetics, whereas the longer blinking is better described by a power law. These observations can be interpreted as arising from environmental relaxation processes and/or changes in the emitter and demonstrate the wide distribution of photophysical behaviours that can be observed among the individual molecules of a polymer sample. The relevance of these studies to the application of polymer materials for solar harvesting is highlighted.

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