Abstract
A comparative investigation for the versatility of sp(2)-hybridized trivalent triel-containing molecules to engage in (+/-)pi-hole interactions with Lewis base, Lewis acid, sigma-hole-containing molecules, and lp-hole-containing molecules was dwelled using quantum mechanical calculations. According to the results, it was found that the (-)pi-hole interactions were more favorable than the (+)pi-hole ones, with larger negative interaction energies and shorter intermolecular distance. (+)pi-hole interactions with lp-hole-containing molecules were observed with larger substantial interaction energies than Lewis acids, and sigma-hole-containing molecules varied from -0.65 to -5.18 kcal/mol. Quantum theory of atoms in molecules and noncovalent interaction index analyses revealed the noncovalent nature for (+/-)pi-hole interactions. As well, symmetry-adapted perturbation theory-based energy decomposition analysis affirmed that electrostatic and dispersion forces controlled the (-)pi-hole interactions, whereas the (+)pi-hole analogs were dominated by dispersion forces only. These findings will be of advantage to the forthcoming studies in the materials and supramolecular chemistry.