Poly(3-hexylthiophene) Molecular Bottlebrushes via Ring-Opening Metathesis Polymerization: Macromolecular Architecture Enhanced Aggregation

We report a facile synthetic strategy based on a grafting through approach to prepare well-defined molecular bottlebrushes composed of regioregular poly(3-hexylthiophene) (rr-P3HT) as the conjugated polymeric side chain. To this end, the exo-norbornenyl-functionalized P3HT macromonomer was synthesized by Kumada catalyst transfer polycondensation (KCTP) followed by postpolymerization modifications, and the resulting conjugated macromonomer was successfully polymerized by ring-opening metathesis polymerization (ROMP) in a controlled manner. The P3HT molecular bottlebrushes display an unprecedented strong physical aggregation upon drying during recovery, as verified by several analyses of the solution and solid states. This remarkably strong aggregation behavior is attributed to a significant enhancement in the number of pi-pi interactions between grafted P3HT side chains, brought about due to the bottlebrush architecture. This behavior is qualitatively supported by coarse-grained molecular dynamics simulations.