Electrochemically Triggered Supramolecular Polymerization Under Kinetic Control

ABSTRACT 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.