Triplet-Triplet Energy Transfer: A Simple Strategy for an Efficient Visible Light-Induced Photoclick Reaction

Photoclick reactions combine the advantages offered by light-driven processes and classical click chemistry and have found applications ranging from surface functionalization, polymer conjugation, photo-crosslinking, and protein labeling. Despite these advances, the dependency of most of the photoclick reactions on UV light poses a severe obstacle for their general implementation, as this light can be absorbed by other molecules in the system resulting in their degradation or unwanted reactivity. However, the development of a simple and efficient system to achieve bathochromically shifted photoclick transformations remains challenging. Here, we introduce triplet-triplet energy transfer as a fast and selective way to enable visible light-induced photoclick reactions. Specifically, we show that 9,10-phenanthrenequinones (PQs) can efficiently react with electron-rich alkenes (ERAs) in the presence of a catalytic amount (as little as 5 mol %) of photosensitizers. The photocycloaddition reaction can be achieved under green (530 nm) or orange (590 nm) light irradiation, representing a bathochromic shift of over 100 nm as compared to the classical PQ-ERAs system. Furthermore, by combining appropriate reactants, we establish an orthogonal, blue and green light-induced photoclick reaction system in which the product distribution can be precisely controlled by the choice of the color of light. Efficient triplet-sensitized photoclick reactions of 9,10-phenanthrenequinone with electron-rich alkenes is introduced. Photocycloadditions are achieved at low concentrations of triplet photosensitizers under green or orange light, exhibiting a significant bathochromic shift of over 100 nm compared to conventional systems. This method enables precise control of product distribution using orthogonal blue and green light-induced photoclick reactions. image