Novel and Polynuclear K- and Na-Based Superalkali Hydroxides as Superbases Better Than Li-Related Species and Their Enhanced Properties: An Ab Initio Exploration

[Image: see text] Hydroxides of superalkalis (particularly, K- and Na-related species) are shown for the first time to function as superbases. A new small series of hydroxides (XM(n+1)OH) is designed based on superalkali species (XM(n+1)) where M (K and Na) is alkali metal atoms, n is the maximal formal valence of the central atom X (F, O, and N), and n ≥ 1. To probe whether such fascinating polynuclear superalkali hydroxides (SAHs), especially the K- and Na-associated moieties are as basic as the representative alkali metal hydroxides (KOH, NaOH, and LiOH) as well as similar Li-based SAHs, a comprehensive computational exploration (in the gas phase) has been reported using the framework of an ab initio method. The ab initio calculations reveal that both the K- and Na-related SAHs consisting of larger gas-phase proton affinity (PA) and gas-phase basicity (GB) values demonstrate stronger basic character compared to the LiOH and Li-based SAHs. However, the available SAHs act as strong bases as well as superbases; among the proposed K- and Na-based SAHs, remarkably, the OK(3)OH moiety having the highest PA (1168.4 kJ/mol) and GB (1146.9 kJ/mol) values shows the evidence of the strongest basicity (i.e., superbase/hyperbase), which exceed enough (ΔPA: 142.1 kJ/mol and ΔGB: 146.9 kJ/mol) the IUPAC-defined superbasicity threshold values (PA: 1026.3 kJ/mol and GB: 1000 kJ/mol) of 1,8-bis(dimethylamino)naphthalene (DMAN). Furthermore, theoretical signatures have been predicted via the electronic structure calculation approach in probing the dissociation energy, ionization potential, electron affinity, HOMO–LUMO gap, and chemical hardness as well as the NCI plot and QTAIM tools are used for the bonding feature analysis and such parameters are well linked with the basicity analyzing parameters. In this study, the ab initio-based computational experiments provide some new insights into the basicity features and understanding of the structural and electronic features of a small series of designed K- and Na-related SAHs. Design and synthesis of such theoretically examined SAHs may pave alternative routes for the experimentally rewarding applications.