Energy migration in the aromatic vinyl polymers. 5. Poly(2-vinyl naphthalene) and polystyrene

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Abstract

Electronic energy migration in pure poly(2-vinyl naphthalene) (P2VN) is analyzed in terms of a theory for three-dimensional transport and trapping in a homogeneous system of randomly distributed chromophores. A simpler theory for 3-D transport on a spatially periodic lattice, which was applied previously to polystyrene (PS) gave self-contradictory results for P2VN because of higher transport rates in P2VN. The fraction of rings in excimer-forming sites (EFS) in pure P2VN, analyzed by the former theory, is found to be 0.072 – moderately larger than the single-chain fraction of 0.026. In contrast, the EFS ring fraction in pure PS was 0.33, much larger than the single-chain fraction of 0.051. This reflects the reduced probability, relative to a phenyl ring pair, of packing a naphthyl ring pair into the necessary sandwich arrangement in the pure polymers. Energy migration in very dilute, miscible blends containing P2VN is analyzed by a one-dimensional transport model, which was applied previously to similar blends containing PS. The nearest-neighbor migration rates obtained from the data for both P2VN and PS are about one hundred times higher than the expected dipole–dipole rates. This suggests that (1) migration is not limited to nearest-neighbor rings, (2) the morphology of the dilute blends does not consist of isolated chains of the aromatic vinyl polymers, or (3) short-range electronic interactions other than dipole–dipole are involved in energy migration.

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