Multilayer films for photon upconversion-driven photoswitching†

Photoswitchable materials are of significant interest for diverse applications from energy and data storage to additive manufacturing and soft robotics. However, the absorption profile is often a limiting factor for practical applications. This can be overcome using indirect excitation via complementary photophysical pathways, such as triplet sensitisation or photon upconversion. Here, we demonstrate the use of triplet–triplet annihilation upconversion (TTA-UC) to drive photoswitching of the energy storing photoswitch norbornadiene–quadricyclane (NBD–QC) in the solid-state. A photoswitchable bilayer polymer film, incorporating the TTA-UC sensitiser–emitter pair of platinum octaethylporphyrin (PtOEP) and 9,10-diphenylanthracene (DPA), was used to trigger the photoinduced [2+2] cycloaddition of NBD to form QC using visible instead of UV light. The isolated TTA-UC film showed green-to-blue upconversion, with a competitive upconversion efficiency of (1.9 ± 0.1%) for the solid-state in air. Direct photoswitching of the isolated NBD film was demonstrated with a narrow UV light source (340 nm). However, in the bilayer film, spectral overlap between the upconverted blue emission in the TTA-UC film and the absorbance band of the NBD film resulted in indirect photoswitching using visible green light (532 nm, 1 W cm⁻²), thus extending the spectral operational window of the photoswitching film. The results demonstrate proof-of-feasibility of TTA-UC-promoted photoswitching in the solid-state, paving the way for potential applications in light-harvesting devices and smart coatings, using a wider selection of irradiation wavelengths.