Controlling the primary sequence of synthetic polymers remains a grand challenge in chemistry. Herein, we will discuss Nature-inspired independent strategies to attain sequence-controlled polymers. In a first route, we demonstrate that donor-acceptor alternating copolymers can be prepared using ring-opening metathesis polymerization (ROMP) of a strained unsymmetrical 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 in the form or aryl/perfluoroaryl interaction are utilized to pre-organize and direct reactants for pressure-induced polymerization.  Although different in scope, both approaches 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 methods toward sequence-controlled polymerizations

ACS Spring 2022

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