Cyclic polyacetylene.

Here we demonstrate the synthesis of cyclic polyacetylene (c-PA), or [∞]annulene, via homogeneous tungsten-catalysed polymerization of acetylene. Unique to the cyclic structure and evidence for its topology, the c-PA contains >99% trans double bonds, even when synthesized at -94 °C. High activity with low catalyst loadings allows for the synthesis of temporarily soluble c-PA, thus opening the opportunity to derivatize the polymer in solution. Absolute evidence for the cyclic topology comes from atomic force microscopy images of bottlebrush derivatives generated from soluble c-PA. Now available in its cyclic form, initial characterization studies are presented to elucidate the topological differences compared with traditionally synthesized linear polyacetylene. One advantage to the synthesis of c-PA is the direct synthesis of the trans-transoid isomer. Low defect concentrations, low soliton concentration, and relatively high conjugation lengths are characteristics of c-PA. Efficient catalysis permits the rapid synthesis of lustrous flexible thin films of c-PA, and when doped with I2, they are highly conductive (398 (±76) Ω-1 cm-1).