The potentiality of sp3-hybridized chalcogen-containing molecules to participate in lone-pair (lp) hole interactions was reported for the first time. lp hole interactions were characterized and compared to σ-hole ones for OF2 and SF2 molecules as a case study. Various quantum mechanical calculations, including molecular electrostatic potential (MEP), maximum positive electrostatic potential (V s,max), point of charge (PoC), symmetry-adapted perturbation theory (SAPT), quantum theory of atoms in molecule (QTAIM), and reduced density gradient-noncovalent interaction (RDG-NCI) calculations, were carried out. The more significant findings to emerge from this study are the following: (i) the V s,max calculation was proved to be an unreliable method to determine the precise σ-hole and lp hole locations. (ii) The maximum positive electrostatic potential of the σ hole and lp hole was found to be at the F-Chal···PoC angle (θ) of 180° and at the centroid of XYlp plane, respectively. (iii) Lewis basicity has a significant effect on the strength of σ-hole and lp hole interactions. (iv) The studied molecules more favorably interact with Lewis bases via the σ hole compared to the lp hole, and (v) stabilization of the σ-hole and lp hole interactions stems from the electrostatic and dispersion forces, respectively.
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