Superatomic Chelates: The Cases of Metal Aza-Crown Ethers and Cryptands.

Li, Na, and Mg+-coordinated hexaaza-18-crown-6 ([18]aneN6) and 1,4,7-triazacyclononane ([9]aneN3), Li[1.1.1]cryptand, and Na[2.2.2]cryptand species possess a diffuse electron in a quasispherical s-type orbital. They populate expanded p-, d-, f-, and g-shape orbitals in low-lying excited states and hence are identified as "superatoms". By means of quantum calculations, their superatomic shell models are revealed. The observed orbital series of M([9]aneN3)2 and M[18]aneN6 (M = Li, Na, Mg+) are identical to the 1s, 1p, 1d, 1f, 2s, and 2p. The electronic spectra of Li[1.1.1]cryptand and Na[2.2.2]cryptand were analyzed up to the 1f1 configuration, and their transitions were found to occur at lower energies compared to their aza-crown ethers. The introduced superatomic shell models in this work closely resemble the Aufbau principle of "solvated electrons precursors". All reported alkali metal complexes bear lower ionization potentials than any atom in the periodic table; thus, they can also be recognized as "superalkalis".