Polyacetylene‐Based Asymmetric Bicyclic Polymer by Blocking‐Cyclization Technique

A rare asymmetric bicyclic polymer containing different length of conjugated polyacetylene segments is synthesized by metathesis cyclopolymerization‐mediated blocking‐cyclization technique. The size of each single ring differs from each other, and the unique cyclic polymer topology is controlled by adjusting the feed ratio of monofunctional monomer to catalyst. The topological difference between linear and bicyclic polymers is confirmed by several techniques, and the visualized morphology of asymmetric bicyclic polymer is directly observed without tedious post‐modification process. The photoelectric and thermal properties of polymers are investigated. This work expands the pathway for the derivation of cyclic polymers, and such unique topological structure enriches the diversity of cyclic polymer classes. Polyacetylene‐based bicyclic polymer with asymmetric cyclic topology is synthesized by metathesis cyclopolymerization‐mediated blocking‐cyclization technique, and the unique molecular topology is directly observed without tedious post‐modification process.