The σ-hole and π-hole of the protonated 2-halogenated imidazolium cation (XC3H4N2+; X = F, Cl, Br, I) were investigated and analyzed. The monomers of (CH3)3SiY(Y=F, Cl, Br, I), considered as the Lewis base, were combined with the σ-hole and π-hole of XC3H4N2+ to form the σ-hole and π-hole interactions in the bimolecular complexes (CH3)3SiY · · · XC3H4N2+ and (CH3)3SiY · · · C3(X)H4N2+(X/Y=F, Cl, Br, I), respectively. For both the σ-hole and π-hole interactions, the equilibrium geometries of complexes show regular changes according to the sequence of heavy sequence of the noncovalent interaction acceptors and donors. The electrostatic energy is the main contribution in the formation of both kinds of interactions, it has linear relations with the V S,max values of σ-hole and the V' S,max values of π-hole. Both the σ-hole and π-hole interactions belong to the closed-shell and noncovalent interactions. The π-hole interactions are stronger than the σ-hole interactions. For the π-hole interactions, the contribution percents of the dispersion energies are somewhat greater than those of the σ-hole interactions, while it is contrary for the polarization energy. Graphical Abstract The protonated 2-halogenated imidazolium cation as the noncovalent interaction donor: the σ-hole and π-hole interactionsᅟ.
Keywords: Noncovalent interaction; Protonated 2-halogenated imidazolium cation; π-hole interaction; σ-hole interaction.