LAUSR

Cyclometalated Ir(III) complexes are often chosen as catalysts for challenging photoredox and triplet-triplet-energy-transfer (TTET) catalyzed reactions, and they are of interest for upconversion into the ultraviolet spectral range. However, the triplet energies of commonly employed Ir(III) photosensitizers are typically limited to values around 2.5-2.75 eV. Here, we report on a new Ir(III) luminophore, with an unusually high triplet energy near 3.0 eV owing to the modification of a previously reported Ir(III) complex with isocyanoborato ligands. Compared to a nonborylated cyanido precursor complex, the introduction of B(C6F5)3 units in the second coordination sphere results in substantially improved photophysical properties, in particular a high luminescence quantum yield (0.87) and a long excited-state lifetime (13.0 μs), in addition to the high triplet energy. These favorable properties (including good long-term photostability) facilitate exceptionally challenging organic triplet photoreactions and (sensitized) triplet-triplet annihilation upconversion to a fluorescent singlet excited state beyond 4 eV, unusually deep in the ultraviolet region. The new Ir(III) complex photocatalyzes a sigmatropic shift and [2 + 2] cycloaddition reactions that are unattainable with common transition metal-based photosensitizers. In the presence of a sacrificial electron donor, it furthermore is applicable to demanding photoreductions, including dehalogenations, detosylations, and the degradation of a lignin model substrate. Our study demonstrates how rational ligand design of transition-metal complexes (including underexplored second coordination sphere effects) can be used to enhance their photophysical properties and thereby broaden their application potential in solar energy conversion and synthetic photochemistry.