Conjugated [5]Cumulene Polymers Enabled by Condensation Polymerization of Propargylic Electrophiles.

Cumulenes, sp -hybridized carbon motifs featuring consecutive double bonds, have rarely been explored as π-elements for conjugated polymers. Long cumulenic conjugated polymers can serve as models for approaching carbyne, an intriguing yet elusive carbon allotrope. However, their synthesis is notoriously difficult due to intrinsic instability. To date, only few [3]cumulene-based polymers have been synthesized, mostly relying on surface chemistry. Higher cumulene-based polymers remain unknown. Here, we present a "meet in the middle" strategy to overcome this challenge and synthesize high-molecular-weight, stable, and solution-processable conjugated [5]cumulene polymers ( M w up to 67.9 kg/mol). Our approach involves a new polymerization method called step-growth condensation polymerization of propargylic electrophiles (step-growth CPPE). The structures and molecular weights of the cumulenic polymers are established by various spectroscopic methods, including a comparative analysis of a discrete oligomer series. By introducing ortho -substituents on the aryl side groups, we successfully address the stability-conjugation dilemma. Electronic communication between cumulene units is found to be contingent upon the aromaticity of the π-spacers, enabling flexible energy-level adjustment and new narrow band gap polymers. The synthetic methodology and structure-property relationship established in this work serve as the starting points for the exploration of this fascinating family of sp -carbon-rich materials.