A series of M2+(H5Aza222)–M′– (M = Be, Mg, Ca; M′ = Li, Na, K) alkalides that contain alkaline earth metal cations complexed by the H5Aza222– cage have been investigated using the CAM-B3LYP method. These alkaline earth-based alkalides not only present unusual structural features but also exhibit extraordinarily large static first hyperpolarizabilities (β0) up to 1.98 × 105 au. By comparing the β0 values among alkalides with various complexants, the Aza222 cage is found to be preferable to the previously investigated calix[4]pyrrole and n6adamanzane (n = 2, 3) complexants in enhancing the first hyperpolarizabilities of alkalides. In addition, the relationships between the β0 values of M2+(H5Aza222)–M′– and the atomic number of the M′– anion, the atomic number of the M2+ cation, and the M–M′ distance are explored.
