Spatially Controlled UV Light Generation at Depth using Upconversion Micelles

UV light can trigger a plethora of useful photochemical reactions for diverse applications, including photocatalysis, photopolymerization, and drug delivery. These applications typically require penetration of high-energy photons deep into materials, yet delivering these photons beyond the surface is extremely challenging due to absorption and scattering effects. Triplet-triplet annihilation upconversion (TTA-UC) shows great promise to circumvent this issue by generating high-energy photons from incident lower-energy photons. However, molecules that facilitate TTA-UC usually have poor water solubility, limiting their deployment in aqueous environments. To address this challenge, a nanoencapsulation method is leveraged to fabricate water-compatible UC micelles, enabling on-demand UV photon generation deep into materials. Two iridium-based complexes are presented for use as TTA-UC sensitizers with increased solubilities that facilitate the formation of highly emissive UV-upconverting micelles. Furthermore, this encapsulation method is shown to be generalizable to nineteen UV-emitting UC systems, accessing a range of upconverted UV emission profiles with wavelengths as low as 350 nm. As a proof-of-principle demonstration of precision photochemistry at depth, UV-emitting UC micelles are used to photolyze a fluorophore at a focal point nearly a centimeter beyond the surface, revealing opportunities for spatially controlled manipulation deep into UV-responsive materials.