N₄Mg₆M (M = Li, Na, K) superalkalis for CO₂ activation

Superatoms have exciting properties, including diverse functionalization, redox activity, and magnetic ordering, so the resulting cluster-assembled solids hold the promise of high tunability, atomic precision, and robust architectures. By utilizing adamantane-like clusters as building blocks, a new class of superatoms N₄Mg₆M (M = Li, Na, K) is proposed here. The studied superalkalis feature low adiabatic ionization energies, an antibonding character in the interactions between magnesium and nitrogen atoms, and highly delocalized highest occupied molecular orbital (HOMO). Consequently, the N₄Mg₆M superalkalis might easily lose their HOMO electrons when interacting with superhalogen electrophiles to form stable superatom [superalkali]⁺[superhalogen]^- compounds. Moreover, the studied superalkalis interact strongly with carbon dioxide, and the resulting N₄Mg₆M/CO₂ systems represent two strongly interacting ionic fragments (i.e., N₄Mg₆M⁺ and CO₂ ^-). In turn, the electron affinity of the N₂ molecule (of -1.8 eV) is substantially lower than that observed for carbon dioxide (EA = -0.6 eV) and consequently, the N₂ was found to form the weakly bound [N₄Mg₆M][N₂] complex rather than the desired ionic [N₄Mg₆M]⁺[N₂]^- product. Thus, the N₄Mg₆M superalkalis have high selectivity over N₂ when it comes to CO₂ reduction and also are themselves stable. We believe that the results described within this paper will be useful for understanding CO₂ activation, which is the first step for producing fuels from CO₂. Moreover, we demonstrate that designing novel superatomic systems and exploring their physicochemical features might be used to create desirable functional materials.