Electrochemical Postpolymerization Modification and Deconstruction of Macromolecules.

Electrolysis is an emerging approach to polymer postpolymerization modification, deconstruction, and depolymerization. Electrochemical reactions are particularly appealing for macromolecular transformations because of their high selectivity, ability to be externally monitored, and intrinsic scalability. Despite these desirable features and the recent resurgent use of small-molecule electrochemical reactions, the development of macromolecular electrolysis has been limited. Herein, we highlight recent examples of polymer transformations driven by heterogeneous redox chemistry. Throughout our exploration of macromolecular electrolysis, we provide our perspective on opportunities for continued investigation in this nascent field. Specifically, we highlight how targeted reaction development through deeper mechanistic insight will expand the scope of materials that can be (de)constructed with electrochemical methods. As this insight is developed, we expect macromolecular electrolysis to emerge as a high-functioning and complementary tool for macromolecular functionalization and deconstruction.