Radical Stitching Polymerization and Its Alternating Copolymerization.

Polymers possessing saturated fused polycycles in the main chain repeating unit have been underexplored despite their potential utility based on their expected properties such as high rigidity, chemical resistance, transparency, and thermal stability. In this regard, herein, we developed a radical stitching polymerization of styryl vinyl ketones for the synthesis of polyketones possessing saturated fused bicyclic repeating units. The polymerization proceeded smoothly with a high degree of stitching efficiency in a chain-growth manner under free radical conditions.

Synthesis of Poly(arylenevinylene)s by Rhodium-Catalyzed Stitching Polymerization/Alkene Isomerization.

Poly(arylenevinylene)s constitute an important class of π-conjugated polymers for their potential utility as optoelectronic materials. Herein, we developed a sequence of rhodium-catalyzed stitching polymerization of 1,2-dialkynyl(hetero)arenes and aromatization-driven alkene isomerization for the synthesis of new poly(arylenevinylene)s. The polymerization and subsequent alkene isomerization proceeded smoothly with high degree of stitching efficiency by employing a Rh/tfb complex as the catalyst, and not only diynes but also triynes and tetraynes could be polymerized to give poly(arylenevinylene)s that are not easily accessible by existing synthetic methods.