Alkalized borazine: A simple recipe to design closed‐shell superalkalis

Superalkalis are hypervalent species, possessing smaller ionization energy (IE) than alkali metal. These species are typically designed by electronegative atoms with excess electropositive ligands. Typical examples include FLi₂, OLi₃, NLi₄, etc. Herein, we study successive alkali metal substitution at H atoms in borazine (B₃N₃H₆). Our B3LYP and MP2 calculations demonstrate that the vertical ionization energy (VIE) of B₃N₃H_6‐xLi_x decreases with the increase in x for x = 1–6. For x ≥ 4, the VIE of B₃N₃H_6‐xLi_x becomes lower than that of Li atom, thereby indicating their superalkali nature. More interestingly, all these species are planar with closed‐shell structure such that the NICS_zz value at the ring's center is reduced. We have also studied B₃N₃M₆ (M = Li, Na, and K) species and found that the VIE is further reduced in case of Na and K substitutions. These findings should suggest a simple yet effective route to the design of species with lower ionization energies than alkali metal.