To date, methods to engineer polymers with precise functional group positioning generally lead to ill-defined architectures, impeding both crystallization and self-assembly. Iterative synthetic routes are promising to achieve well-defined materials, yet they can be time-consuming and often require extensive product purification. Balanced cost- and time-effective strategies are needed to access novel materials. Herein, we disclose two independent methods toward obtaining sequence control: in a first route, we demonstrate the controlled synthesis of alternating copolymers prepared using ring-opening metathesis polymerization (ROMP) of a strained unsymmetrical and ‘electronically-ambiguous’ donor-acceptor cyclophanediene. The ROMP proceeds in wake of both steric and electronic encumbrance to afford donor-acceptor conjugated polymers. In a second separate strategy, supramolecular interactions are utilized to pre-organize and direct reactants for pressure-induced topochemical solid-state polymerizations, wherein noncovalent interactions aid in precise C—C bond formation. Although the two approaches are different in scope, both rely on retrosynthetic design to engineer ‘locked-in’ A-B monomeric units in a precise manner. Our approaches are significant in a field striving to synthesize well-defined and sequence-specific materials.

Synthetic organic and supramolecular strategies toward sequence-controlled polymerizations

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.