Luminescent and Photoredox‐Active Molybdenum(0) Complexes Competitive with Isoelectronic Ruthenium(II) Polypyridines

Ruthenium(II) complexes with chelating polypyridine ligands are among the most frequently investigated compounds in photophysics and photochemistry, owing to their favorable luminescence and photoredox properties. Equally good photoluminescence performance and attractive photocatalytic behavior is now achievable with isoelectronic molybdenum(0) complexes. The zero-valent oxidation state of molybdenum is stabilized by carbonyl or isocyanide ligands, and metal-to-ligand charge transfer (MLCT) excited states analogous to those in ruthenium(II) complexes can be established. Microsecond MLCT excited-state lifetimes and photoluminescence quantum yields up to 0.2 have been achieved in solution at room temperature, and the emission wavelength has become tunable over a large range. The molybdenum(0) complexes are stronger photoreductants than ruthenium(II) polypyridines and can therefore perform more challenging chemical reductions. The triplet nature of their luminescent MLCT states allows sensitization of photon upconversion via triplet-triplet annihilation, to convert low-energy input radiation into higher-energy output fluorescence. This review summarizes the current state of the art concerning luminescent molybdenum(0) complexes and highlights their application potential. Molybdenum is roughly 140 times more abundant and far cheaper than ruthenium, hence this research is relevant in the greater context of finding more sustainable alternatives to using precious and rare transition metals in photophysics and photochemistry.