Redox-Active Heteroatom-Functionalized Polyacetylenes.

Abstract

The discovery of metallic conductivity in polyacetylene [-HC=CH-]n upon doping represents a landmark achievement. However, the insolubility of polyacetylene and a dearth of methods for its chemical modification have limited its widespread use. Here, we employ a ring-opening metathesis polymerization (ROMP) protocol to prepare functionalized polyacetylenes (fPAs) bearing: (1) electron-deficient boryl (-BR2 ) and phosphoryl (-P(O)R2 ) side chains; (2) electron-donating amino (-NR2 ) groups, and (3) ring-fused 1,2,3-triazolium units via strain-promoted Click chemistry. These functional groups render most of the fPAs soluble and can lead to intense light absorption across the visible to near-IR region. Also, the presence of redox-active boryl and amino groups leads to opposing near-IR optical responses upon (electro)chemical reduction or oxidation. Some of the resulting fPAs show greatly enhanced air stability when compared to known polyacetylenes. Lastly, these fPAs can be cross-linked to yield network materials with the full retention of optical properties.