ja1c09827_si_001.pdf (22.74 MB)
Rhodium-Catalyzed Stitching Polymerization of Alkynylsilylacetylenes
journal contributionposted on 2021-10-29, 19:34 authored by Sho Ikeda, Yuki Hanamura, Hirokazu Tada, Ryo Shintani
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 π-conjugated 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.
readily prepared alkynylsilylacetylenespolymerization proceeded smoothlycatalyzed stitching polymerizationbridged repeating unitsalkynylsilylacetylenes polymers possessingstitching mannerbridged πtfb complextetraynes couldstitched polymerssolvents couldpotential utilityphysical propertiesoptoelectronic materialsobtained polymersnew πimportant classgive polymersexisting methodsdifferent typesconjugated polymerscharacteristic featuresalso triynesalso investigated