Controlling thermal reactivity with different colors of light

The ability to switch between thermally and photochemically activated reaction channels with an external stimulus constitutes a key frontier within the realm of chemical reaction control. Here, we demonstrate that the reactivity of triazolinediones, powerful coupling agents in biomedical and polymer research, can be effectively modulated by an external photonic field. Specifically, we show that their visible light-induced photopolymerization leads to a quantitative photodeactivation, thereby providing a well-defined off-switch of their thermal reactivity. Based on this photodeactivation, we pioneer a reaction manifold using light as a gate to switch between a UV-induced Diels–Alder reaction with photocaged dienes and a thermal addition reaction with alkenes. Critically, the modulation of the reactivity by light is reversible and the individually addressable reaction pathways can be repeatedly accessed. Our approach thus enables a step change in photochemically controlled reactivity, not only in small molecule ligations, yet importantly in controlled surface and photoresist design.