The Thiol-Thioester Exchange in Network and Linear Polymers

Dynamic bonds are covalent linkages which, if given specific stimuli, can form an equilibrium between exchanging reactants and their products. Recent work by our lab has developed dynamic functional groups which can be seemlessly incorporated into network or linear polymers and harnesses the supurb reactivity and chemoselectivity of thiyl radicals and thiolate anions. These dynamic functionalities act as crosslinks in network polymers or in the backbone of linear polymers and are easily adapted to various stimuli including light, heat, or chemical. Here we show recent developments towards the formation of dynamic liquid crystalline networks and thioester-based networks both responsive towards light in order to develop shape shifting and remoldable photopolymers. Additionally, we demonstrate a sequence shifting, dynamic thioester-linked DNA-like polymer by implementing an covalently exchangeable thioester backbone. We believe that the broad implementation of this chemistry demonstrates the breadth of this approach towards the formation of smart, responsive polymers.