Polymers possessing a silicon-bridged π-conjugated repeating unit constitute an important class of compounds for their potential utility as optoelectronic materials. Herein we developed a rhodium-catalyzed stitching polymerization of nonconjugated and readily prepared alkynylsilylacetylenes for the synthesis of new πconjugated polymers with ladder-type silicon-bridged repeating units. The polymerization proceeded smoothly by employing a Rh/ tfb complex as the catalyst, and not only diynes but also triynes and tetraynes could be polymerized in a stitching manner to give polymers that are inaccessible by existing methods. The solubility of the polymers in different types of solvents could be controlled by introducing appropriate functional groups on the silicon atoms, and sequence-controlled functionalized polyacetylenes could be accessed by protodesilylation of the stitched polymers. Physical properties of the obtained polymers were also investigated to understand their characteristic features.

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

Anionic stitching polymerization of styryl(vinyl)silanes has been developed for the synthesis of new type of silicon- and carbon-containing polymers possessing fused sila-bicyclic structures in the main chain. The obtained polymers...

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.