Intermolecular order of poly-(2,5-dimethyl-para-phenylene vinylene) and poly-(para-phenylene vinylene) - A comparison

Abstract

Poly-(para-phenylene vinylene) (2b, PPV) and poly-(2,5 -dimethyl-para-phenylenevinylene) (Ib) were prepared via the formation of a double bond by thermal elimination of an octylsulfinyl side group at 200 degreesC under vacuum. X-Ray diffraction experiments revealed a certain degree of long-range order within both polymers. However, considerable differences in the diffraction pattern were observed, the packing of the polymer chains within the bulk structure being responsible for these differences. Within the crystal structure of 2b. neighbouring PPV chains pack in a zig-zag arrangement (herringbone pattern). Analysis of the diffraction pattern of Ib on the basis of the crystal structure of a model compound (2,5,2 ' ,5 ' -tetramethylstilbene) revealed that the molecular planes of neighbouring polymer chains pack parallel to each other. A model for the crystal structure of Ib is given. The change of packing from a herringbone to a parallel arrangement of the molecular planes is related to the introduction of methyl groups as side chains to PPV