Sudden, "step" electron capture by conjugated polymers

J Phys Chem A. 2011 Oct 27;115(42):11615-23. doi: 10.1021/jp205790k. Epub 2011 Oct 3.


Data showing significant time-resolution-limited "step" capture of electrons following radiolysis by 7 - 10 ps electron pulses in a series of different length and different concentration conjugated polyfluorene polymers in tetrahydrofuran (THF) are presented. At the highest concentration, ∼48 mM in repeat units for lengths from 20 to 133 fluorenes, ∼30% of the electrons formed during pulse radiolysis were captured in the step, with a constant efficiency per repeat unit. Step capture per repeat unit (q = 6.9 M(-1)) is 60% of the presolvated electron capture efficiency previously reported for biphenyl in THF, giving capture per polymer molecule 12-80 times larger than that for biphenyl at the same concentration. This increase in capture efficiency is large compared to the rate constant per repeat unit for diffusion-limited electron attachment to the same molecules, which is 13% of that of a single unit of fluorene. Plausible mechanisms of this fast capture are explored. It is shown that both capture of quasi-free and localized presolvated electrons can adequately explain the observations. The large yield of radical anions at low concentration of polyfluorene enables observation of subsequent chemistry on the picosecond time scale in these systems, which would otherwise been limited by diffusional attachment to the nanosecond regime.