Making Mo(0) a Competitive Alternative to Ir(III) in Phosphors and Photocatalysts.

Iridium is used in commercial light-emitting devices and in photocatalysis but is among the rarest stable chemical elements. Therefore, replacing iridium(III) in photoactive molecular complexes with abundant metals is of great interest. First-row transition metals generally tend to yield poorer luminescence behavior, and it remains difficult to obtain excited states with redox properties that exceed those of noble-metal-based photocatalysts. Here, we overcome these challenges with a nonprecious second-row transition metal. Tailored coordination spheres for molybdenum(0) lead to photoluminescence quantum yields that rival those of iridium(III) complexes and photochemical reduction reactions not normally achievable with iridium(III) become possible. These developments open new perspectives for replacing noble metals in lighting applications with Earth-abundant metals and for advancing metal-based photocatalysis beyond current limits.