Electron Presolvation in Tetrahydrofuran-Incorporated Supramolecular Sodium Entities

Alkali metal atoms can repopulate their valence electrons toward solvation due to impact from solvents or microsurroundings and provide the remaining alkali metal cations for coordinating with a variety of specific solvents, forming various electron-expanded complexes or solvated ionic pairs with special interactions. Such special solute-solvent interactions not only affect their electronic structures but also enable the formation of entirely new species. Taking Na(THF) (n = 1-6, THF = tetrahydrofuran) and Na₂@THF complexes as typical representatives, density functional theory calculations are carried out to explore the solvation of a sodium atom and its dimer in THF and characterize their complexes as solvent-incorporated supramolecular entities and particularly valence electron presolvation due to their interaction with solvent THF. Electron presolvation is caused by the Pauli repulsion between THF containing a coordinating O atom with a lone pair of electrons and the alkali metal Na or Na₂ containing valence electrons, and THF coordination to them forces their valence electrons to redistribute, which can be easily realized in such solvents. Compared with strongly bound valance electrons of alkali metal atoms, THF coordination enables Na or Na₂ electrons to exhibit much more active states (i.e., the presolvated states) featuring small vertical detachment energies of electrons and distorted diffuse distributions in the frames of the generally structured metal cation complexes, acting as the electron-expanded chemical entities. Furthermore, the degree of electron diffusion and the polarity of the Na-Na bond are proportional to the coordination number (n) and the coordination number difference (Δn) between two Na centers in Na₂@THF. The unique properties of such entities are also discussed. This work offers a theoretical support to the supramolecular entities formed by alkali-metal atoms or their dimers with ligands containing O or N and uncovers the unique electron presolvation phenomena and also enriches our understanding of the novel metal atom complexes.