Self-assembly and ring-opening metathesis polymerization of a bifunctional carbonate–stilbene macrocycle

Abstract

A carbonate–stilbene bifunctional macrocycle was readily synthesized, and its assembly was studied by crystallization from several solvents. The macrocycle displayed columnar assembly from less polar solvents (THF and CH₂Cl₂), while a more compact structure was observed from 9 : 1 CH₂Cl₂–acetone. All structures displayed organization through the C–H⋯O hydrogen bonding motif as well as through aryl stacking interactions. Upon dissolution and treatment with Grubbs’ II catalyst, this 30-membered ring underwent entropy-driven ring-opening metathesis polymerization (ED-ROMP) to give a precisely linear alternating A–B–A–B copolymer. This design of a single macrocyclic building block allows the formation of supramolecular self-assembly in the solid-state while affording a linear alternating polymer from solution.