Polymerization of bifunctional dithioester and the conversion into poly(p-phenylene vinylene)s

[Display omitted] •Bifunctional dithioesters are used as precursors for PPV derivatives.•The superbase, t-Bu-P4, is very effective in the polymerization of bifunctional dithioesters.•The precursor polymer is convertible into PPV derivatives by thermal elimination. Poly(p-phenylene vinylene)s (PPVs) are a class of widely studied conjugated polymers which can be synthesized by p-xylylene precursor strategies. In this paper, we report new results of a dithioester precursor route for the synthesis of PPV derivatives. Bifunctional dithioester with p-xylylene leaving group was used as monomer which underwent polymerization to form a precursor bearing one dithioester moiety on each repeat unit. The polymerization was influenced by temperature, solvent and base. The polymerization mechanism was proposed to involve a p-quinodimethane intermediate, similar to those reported in the literature using other starting materials such as alkylhalides, sulfonium, sulfinyl, sulfonyl, xanthate, and dithiocarbamate. The obtained precursors were subject to thermal conversion to form the conjugated structure through elimination of the remaining dithioester moiety. FT-IR, UV–Vis and PL spectroscopies, as well as thermal gravimetric analysis were used to monitor the thermal conversion process and the formation of the conjugated structure. Thus the present method may serve as a new route for the synthesis of PPV derivatives.