Plasma-Assisted Dinitrogen Activation on Small Cobalt Clusters: Co₄ N₉ ⁺ with Enhanced Stability

We have performed a study on the accommodation of nitrogen doping toward superatomic states of transition metal clusters. By reacting cobalt clusters with N₂ in the presence of plasma radiation, a large number of odd-nitrogen clusters were observed, typically Co₃ N_2m-1 ⁺ (m=1-5) and Co₄ N_2m-1 ⁺ (m=1-6) series, showing N≡N bond cleavage in the mild plasma atmosphere. Interestingly, the Co₃ N₇ ⁺ , Co₄ N₉ ⁺ , and Co₅ N₉ ⁺ clusters exhibit prominent mass abundances. First-principles calculation results elucidate the stability of the diverse cobalt nitride clusters and find unique stability of Co₄ N₉ ⁺ with a swallow-kite structure of which four coordinated N₂ molecules causes a significantly enlarged HOMO-LUMO gap, while the single N atom doping gives rise to superatomic states of 1S² 1P³ ||1D⁰ . We reveal an efficient dinitrogen activation strategy by reacting multiple N₂ molecules with cobalt clusters under a plasma atmosphere.