Strategies to Enhance Cyclopolymerization using Third-Generation Grubbs Catalyst

Cyclopolymerization (CP) of 1,6-heptadiyne derivatives using the Grubbs catalysts has been known to afford conjugated polyenes in low yields in dichloromethane (DCM), the most common solvent for olefin metathesis polymerization and a good solvent for typical conjugated polymers. Based on our previous work that showed highly efficient CP using the Grubbs catalysts in tetrahydrofuran (THF), we developed a new polymerization system using weakly coordinating additives with the third-generation Grubbs catalyst in DCM. The polymerization efficiency of various monomers and their controls dramatically increased by adding 3,5-dichloropyridine, yielding polymers with narrow polydispersity indices (PDIs) at low temperatures. These new reaction conditions not only expand the monomer scope by resolving the solubility concerns of conjugated polymers but also more effectively reduced the chain transfer. Consequently, fully conjugated diblock copolymer was successfully prepared. Additionally, kinetic analysis has revealed that low CP efficiency in DCM resulted from the rapid decomposition of the propagating carbene. This decomposition was effectively suppressed by both pyridine additives and THF, suggesting that weakly coordinating additives stabilize the living chain end. Furthermore, we observed that the turnover number of CP was higher at lower temperatures (0-10 degrees C) than at ambient temperatures, consistent with the understanding that the lifetime of a propagating carbene is greater at lower temperatures. Steric protection was also shown to increase the stability of the propagating carbene, as shown by a higher turnover number for the 3,3-dimethyl-substituted 1,6-heptadiyne compared to the nonfunctionalized monomer.