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October 7, 2020

Volume 142, Issue 40

Pages 16903-17208


Controlled Cyclopolymerization of 1,5-Hexadiynes to Give Narrow Band Gap Conjugated Polyacetylenes Containing Highly Strained Cyclobutenes


For decades, cyclopolymerization of α,ω-diyne derivatives has been an effective method to synthesize various soluble polyacetylenes containing five- to seven-membered rings in the backbone. However, cyclopolymerization to form four-membered carbocycles was considered impossible due to their exceptionally high ring strain (∼30 kcal/mol). Herein, we demonstrate the successful cyclopolymerization of rationally designed 1,5-hexadiyne derivatives to afford various polyacetylenes containing highly strained cyclobutenes in each repeat unit. After screening, Ru catalysts containing bulky diisopropylphenyl groups promoted challenging four-membered ring cyclization efficiently from various monomers, enabling the synthesis of high molecular weight (up to 40 kDa) polyacetylenes in a controlled manner. Furthermore, living polymerization allowed for block copolymer synthesis by combining with ring-opening metathesis polymerization as well as block copolymerization of two different 1,5-hexadiyne monomers to give a fully conjugated polyacetylene. These new polymers unexpectedly showed much narrower band gaps than conventional substituted polyacetylenes by >0.2 eV. Interestingly, computational studies showed much smaller bond length alternation in the conjugated backbone containing cyclobutenes, resulting in highly delocalized π electrons along the polymer chain and lower band gaps.


  • Cheol Kang
  • Kijung Jung
  • Sojeong Ahn
  • Tae-Lim Choi





https://pubs.acs.org/toc/jacsat/142/40



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