Rhodium-Catalyzed Stitching Polymerization of 1,5-Hexadiynes and Related Oligoalkynes.

A new mode of polymerization, rhodium-catalyzed stitching polymerization, has been developed for the synthesis of π-conjugated polymers with bridged repeating units from nonconjugated 1,5-hexadiynes containing both terminal and internal alkyne moieties as monomers. The polymerization proceeded smoothly with a high degree of stitching efficiency under mild conditions, and 1,5,9-decatriyne and 1,5,9,13-tetradecatetrayne monomers could also be employed. The present polymerization strategy would be particularly beneficial for the synthesis of polymers consisting of a repeating unit that is difficult to prepare as a stable monomer because it does not require the use of a preformed bridged π-conjugated monomer.