Double-stranded vinyl polymer with transformable side chains synthesized in a metal‒organic framework

Abstract

Post-polymerization modification (PPM) via active ester chemistry is a valuable method for modulating side-chain structures without altering their main-chain topology. Herein, we synthesized a double-stranded vinyl polymer with an active ester by crosslinking radical polymerization within the nanochannels of a metal‒organic framework (MOF) with a pore diameter comparable to that of the duplex. The resulting double-stranded poly(1,1,1,3,3,3-hexafluoroisopropyl acrylate) (DPHFIPA) was readily converted into acrylates and acrylamides with side chains derived from the nucleophile used in the PPM. This approach offers a pathway for creating double-stranded vinyl polymers with repeating units that are otherwise difficult to synthesize, even when MOF-templated polymerization is used. Double-stranded polymers have attracted attention due to their elegant structures and potential properties arising from their topology. In this work, we performed cross-linking polymerization of an active ester acrylate monomer within the nanochannels of a metal‒organic framework (MOF). The spatial constraints in the MOF facilitated the formation of a polymer duplex. Subsequently, transformation of the side chains could be achieved without altering the double-stranded topology, providing a variety of functional vinyl polymer duplexes.