Phosphinate Apical Ligands: A Route to a Water-Stable Octahedral Molybdenum Cluster Complex

Abstract

Recent studies have unraveled the potential of octahedral molybdenum cluster complexes (Mo₆) as relevant red phosphors and photosensitizers of singlet oxygen, O₂(¹Δ_g), for photobiological applications. However, these complexes tend to hydrolyze in an aqueous environment, which deteriorates their properties and limits their applications. To address this issue, we show that phenylphosphinates are extraordinary apical ligands for the construction of Mo₆ complexes. These new complexes display unmatched luminescence quantum yields and singlet oxygen production in aqueous solutions. More importantly, the complex with diphenylphosphinate ligands is the only stable complex of these types in aqueous media. These complexes internalize in lysosomes of HeLa cells, have no dark toxicity, and yet are phototoxic in the submicromolar concentration range. The superior hydrolytic stability of the diphenylphosphinate complex allows for conservation of its photophysical properties and biological activity over a long period, making it a promising compound for photobiological applications.