Conjugation length control in soluble poly[2-methoxy-5-((2'-ethylhexyl)oxy)-1,4-phenylenevinylene] (MEHPPV): synthesis, optical properties, and energy transfer

Abstract

Poly[2-methoxy-5-((2'-ethylhexyl)oxy)-1,4-phenylenevinylene] (MEHPPV) of varying conjugation length was prepared by the selective thermal elimination of one of the substituents in a suitable precursor polymer. The precursor, a dialkoxy poly(1,4-xylylene) derivative with varying amounts of acetoxy and methoxy groups, was prepared by a competitive nucleophilic substitution of the Wessling polyelectrolyte, using methanol and sodium acetate in acetic acid as nucleophiles. Selective thermal elimination (in solution) of the acetate groups alone yielded MEHPPV of varying conjugation lengths. The selective nature of the acetate elimination was confirmed by ¹H NMR spectroscopy. As expected, both the absorption and emission maxima of the eliminated samples shifted to the red with increasing conjugation length. While there was very little difference between the absorption spectra of thin film and solutions of MEHPPV-x, there was a significant bathochromic shift in the emission spectra of the thin films when compared to their dilute solution spectra. Additionally, separate emission from the various oligomers, which are occasionally visible in solution, is absent in thin films. Energy transfer from short to longer conjugated segments, within a single polymer chain in solution, was inferred by comparison of the fluorescence spectra of the partially conjugated polymers with those expected from a system where simultaneous independent emission occurs from a similar collection of noninteracting oligophenylenevinylene (OPV) molecules. The latter was calculated assuming a statistically random substitution/elimination process of the precursor in conjunction with the fluorescence spectral data of OPV's reported by previous workers. The extent of energy transfer increases as the average conjugation length increases. Furthermore, unlike in the model oligomers, in the case of polymers the fluorescence quantum yield in solution rapidly decreases with increase in the average conjugation length.