The steady stream of newly designed ruthenium and molybdenum catalysts for olefin metathesis has allowed the synthesis of polymers with an ever increasing structural control at the molecular level. In particular, the recent development of stereoselective and stereoretentive catalysts has enabled the synthesis of polyalkenamers and conjugated polymers with unprecedented stereoselectivity for the olefins in the backbone. This presentation will highlight the potential of stereoretentive olefin metathesis to access light-responsive all-cis poly(p-phenylene vinylene)s (PPVs). The discussion will focus on the design of monomers and catalysts to obtain all-cis PPVs with desirable molar masses and functionalizable chain ends. The unique reactivity of dithiolate Ru-carbene catalysts will be covered among other catalysts. Finally, the photoresponsive behavior of all cis-PPVs, as well as the effect of olefin stereochemistry on the properties of these polymers will be illustrated with examples including homopolymers and diblock copolymers.

Stereodefined conjugated polymers via stereoretentive olefin metathesis

ACS Fall 2021

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