Near-Infrared Photoinduced Coupling Reactions Assisted by Upconversion Nanoparticles.

We introduce nitrile imine-mediated tetrazole-ene cycloadditions (NITEC) in the presence of upconversion nanoparticles (UCNPs) as a powerful covalent coupling tool. When a pyrene aryl tetrazole derivative (λabs, max =346 nm) and UCNPs are irradiated with near-infrared light at 974 nm, rapid conversion of the tetrazole into a reactive nitrile imine occurs. In the presence of an electron-deficient double bond, quantitative conversion into a pyrazoline cycloadduct is observed under ambient conditions. The combination of NITEC and UCNP technology is used for small-molecule cycloadditions, polymer end-group modification, and the formation of block copolymers from functional macromolecular precursors, constituting the first example of a NIR-induced cycloaddition. To show the potential for in vivo applications, through-tissue experiments with a biologically relevant biotin species were carried out. Quantitative cycloadditions and retention of the biological activity of the biotin units are possible at 974 nm irradiation.