Reversible redox controlled acids for cationic ring-opening polymerization.

Advancements in externally controlled polymerization methodologies have enabled the synthesis of novel polymeric structures and architectures, and they have been pivotal to the development of new photocontrolled lithographic and 3D printing technologies. In particular, the development of externally controlled ring-opening polymerization (ROP) methodologies is of great interest, as these methods provide access to novel biocompatible and biodegradable block polymer structures. Although ROPs mediated by photoacid generators have made significant contributions to the fields of lithography and microelectronics development, these methodologies rely upon catalysts with poor stability and thus poor temporal control. Herein, we report a class of ferrocene-derived acid catalysts whose acidity can be altered through reversible oxidation and reduction of the ferrocenyl moiety to chemically and electrochemically control the ROP of cyclic esters.