Photoinduced polyelectrolyte complexation for the formation of stable films with reversible crosslinking

Thin films formed by complexation of oppositely charged polyelectrolytes have significant potential in applications such as separation membranes, biocompatible or anticorrosion coatings, and drug delivery systems. While layer-by-layer deposition is a reliable method for producing conformal films, this multi-step process limits scalability. In this study, we functionalize polymers with photoactive protecting and crosslinking groups, allowing a one-step approach for preparing polyelectrolyte complex (PEC) films. To achieve this goal, we introduced o-nitrobenzyl and coumarin groups into a polyanion. The o-nitrobenzyl protecting groups can be selectively deprotected upon exposure to 365 nm light, revealing charged pendent groups that initiate polyelectrolyte complexation. Simultaneously, the coumarin units in the copolymers undergo dimerization, enhancing the solvochemical stability of the PEC films. Notably, short-wave UV irradiation (254 nm) enables retrocyclization of the coumarin dimers, returning the PEC film to its uncrosslinked state. These UV-driven deprotection, crosslinking, and de-crosslinking processes provide a versatile and tunable platform for fabricating reversibly crosslinked films. By integrating photoresponsive polymers and reversible covalent linkages, this approach offers new opportunities for designing PEC materials with tunable dynamic properties for advanced applications.