The propensity of halogen‐bearing molecules (XF 3 ) in a T‐shaped geometry to interact with Lewis bases (LBs) and thereby engage in π‐hole interactions in the fashion of F 3 X⋯LBs (where X = Cl, Br, and I; LB = NH 3 , N 2 H 2 , and N 2 ) complexes was studied using diverse ab initio calculations. Moreover, for the first time, the tendency of XF 3 molecules to participate in π‐hole⋯π‐hole interactions through the homo and hetero F 3 X⋯XF 3 complexes was extensively studied. The electrostatic potential analysis outlined the presence of positive regions over the molecular entity of XF 3 molecules, dubbed as π‐hole sites. For all F 3 X⋯LBs and F 3 X⋯XF 3 complexes, negative interaction energy findings were perceived, ranging from −0.32 to −3.82 kcal/mol. Comparatively, higher favorability for the π‐hole interactions over the π‐hole⋯π‐hole ones was noticed through detecting more negative interaction energies for the F 3 X⋯LBs complexes than the like⋯like and unlike F 3 X⋯XF 3 candidates. Moreover, for all the studied interactions, a progressive increment in the interaction energy values was observed with the growth of the atomic size of the halogen atom. For the F 3 X⋯LBs complexes, the MP2 energies were detected, and the findings uncovered that the XF 3 molecules inclined to favorably interact with s p 3 ‐hybridized nitrogen‐bearing Lewis bases, followed by s p 2 ‐ and sp ‐hybridized ones. Interestingly, the analyses of the quantum theory of atoms in molecules and noncovalent interaction index outlined the closed‐shell nature of the studied interactions. Symmetry‐adapted perturbation theory findings proclaimed the dominance of the electrostatic forces within the π‐hole interactions, whereas the π‐hole⋯π‐hole interactions were dominated by the dispersion forces. These annotations will be a basic linchpin for the forthcoming studies concerned with crystal engineering and supramolecular chemistry.
Ibrahim et al. (Thu,) studied this question.