Asymmetric Ion-Pairing in Stereoselective Vinyl Polymerization

Controlling polymer tacticity is a key consideration in macromolecular synthesis due to the impact of stereochemistry on a material’s thermomechanical and optical properties. Recently, inspired by work in small molecule catalysis, asymmetric ion-pairing has emerged as a valuable approach to control the stereochemistry of polymers made through chain growth polymerization of vinyl monomers. This Perspective outlines some of the challenges inherent to polymer stereocontrol as well as highlights recent catalyst development in the area of asymmetric ion-pairing that has enabled control of both the configuration and conformation of vinyl polymers. Several synthetic opportunities and mechanistic questions have been identified that will expand the impact of asymmetric ion-pairing in polymer synthesis.