Photoswitchable Imines Drive Dynamic Covalent Systems to Nonequilibrium Steady States.

Coupling a photochemical reaction to a thermal exchange process can drive the latter to a nonequilibrium steady state (NESS) under photoirradiation. Typically, systems use separate motifs for photoresponse and equilibrium-related processes. Here, we show that photoswitchable imines can fulfill both roles simultaneously, autonomously driving a dynamic covalent system into a NESS under continuous light irradiation. We demonstrate this using transimination reactions, where E -to- Z photoisomerism generates a more kinetically labile species. At the NESS, energy is stored both in the metastable Z -isomer of the imine and in the system's nonequilibrium constitution; when the light is switched off, this stored energy is released as the system reverts to its equilibrium state. The system operates autonomously under continuous light irradiation and exhibits characteristics of a light-driven information ratchet. This is enabled by the dual-role of the imine linkage as both the photochromic and dynamic covalent bond. This work highlights the ability and application of these imines to drive systems to NESSs, thus offering a novel approach in the field of systems chemistry.