Isolation of a Terminal Cobalt Nitride in a Metal–Organic Framework

Transition metal nitrides are reactive intermediates in biological and industrial processes. Chemists have synthesized molecular model complexes of such reactive species to understand their function and electronic requirements for new applications. However, molecular chemistry can suffer from intra- and intermolecular decomposition pathways, which preclude further discovery of unknown reactive species. Metal–organic frameworks offer an opportunity for creating long-lived forms of such species with the vacuum of the pore suppressing degradation while simultaneously enabling substrate access for controlled reactivity studies. Here, we report the characterization of an elusive terminal cobalt nitride species generated through photolysis or thermolysis of a site-isolated cobalt azide within the evacuated metal–organic framework CoN₃-MFU-4l. The first crystal structure of such a species is presented, with vibrational, X-ray absorption, and electron paramagnetic resonance spectroscopies providing further direct evidence for its formation while elucidating its electronic structure. The system additionally enables subsequent reactivity studies with selected substrates, revealing a unique ambiphilic behavior for a metal nitride species.