Electrochemically Triggered Supramolecular Polymerization Under Kinetic Control

Stimuli-responsive supramolecular polymerization with high precision is essential for developing adaptive materials with programmable kinetics and functions. Here, we present a redox-responsive strategy that integrates chemical redox reactions and electrochemical potential to direct the self-assembly of a perylene diimide-histidine (PDI-His). A chemical redox process with sodium dithionite (SDT) rapidly converts kinetically trapped dimeric aggregates (Agg-I) of PDI-His stabilized by intramolecular hydrogen bonding into thermodynamically favored helical nanofibers (Agg-II), enabling the preparation of seeds with tunable lengths. Electrochemical potential application also induces reorganization of Agg-I into Agg-II, accompanied by morphological evolution, and improved conductivity via enhanced π-π stacking. Importantly, the redox-cycle-driven supramolecular reorganization was achieved not only on electrode surfaces through electrochemical stimuli but also through seeded-living supramolecular polymerization using seeds generated via both chemical and electrochemical kinetic pathways, yielding nanofibers with predictable lengths. This combined chemical- and electrochemical-redox approach provides an adaptable platform for controlling pathways in supramolecular polymerization, advancing the design of stimuli-responsive materials for applications in electronics, sensing, catalysis, and bioinspired systems.