A Photorobust Mo(0) Complex Mimicking Os(2,2′-bipyridine)32+ and Its Application in Red-to-Blue Upconversion

Osmium(II) polypyridines are a well-known class of complexes with luminescent metal-to-ligand charge-transfer (MLCT) excited states that are currently experiencing a revival due to their application potential in organic photoredox catalysis, triplet-triplet annihilation upconversion, and phototherapy. At the same time, there is increased interest in the development of photoactive complexes made from Earth-abundant rather than precious metals. Against this background, we present a homoleptic Mo(0) complex with a new diisocyanide ligand exhibiting different bite angles and a greater extent of π-conjugation than previously reported related chelates. This new design leads to deep red emission, which is unprecedented for homoleptic arylisocyanide complexes of group 6 metals. With a 3MLCT lifetime of 56 ns, an emission band maximum at 720 nm, and a photoluminescence quantum yield of 1.5% in deaerated toluene at room temperature, the photophysical properties are reminiscent of the prototypical Os(2,2'-bipyridine)32+ complex. Under 635 nm irradiation with a cw-laser, the new Mo(0) complex sensitizes triplet-triplet annihilation upconversion of 9,10-diphenylanthracene (DPA), resulting in delayed blue fluorescence with an anti-Stokes shift of 0.93 eV. The photorobustness of the Mo(0) complex and the upconversion quantum yield are high enough to generate a flux of upconverted light that can serve as a sufficiently potent irradiation source for a blue-light-driven photoisomerization reaction. These findings are relevant in the greater contexts of designing new luminophores and photosensitizers for use in red-light-driven photocatalysis, photochemical upconversion, light-harvesting, and phototherapy.