Photo-induced absorption spectra of a poly(p-phenylenevinylene) polymer with fluorinated double bonds

We report on the optical and photo-physical properties of a fluorinated poly(p-phenylenevinylene) derivative,
namely poly(2-methoxy-5-[(2-ethylhexyl)oxy]-1,4-phenylenedifluorovinylene) (MEH-PPDFV)
and we compare them with those of the well-known non fluorinated reference system, poly(2-methoxy-
5-[(2-ethylhexyl)oxy]-1,4-phenylenevinylene) (MEH-PPV) synthesized with the same procedure.
Remarkable blue-shifts of absorption and emission spectra of MEH-PPDFV with respect to MEH-PPV
are observed, due to the larger distortion from planarity of the fluorinated species. In addition, the
blue-shift for optical transitions in absorption spectra is more pronounced than in emission ones, since
the molecule conformation in the excited states is more planar than in the ground one.
Microsecond photo-induced absorption spectra of MEH-PPDFV reveal three bands possessing spectral
properties and/or kinetics different from those observed for MEH-PPV. The assignment of these transitions
is provided in terms of free and trapped polarons as well of triplet excitons. Free-polarons have an
intrinsic decay constant of 3 ms, while the trapping dynamics has a longer kinetics of 40 ms. The triplet
exciton, instead, shows a monoexponetial decay behavior of constant about 10 ms.