In the current study, σ‐hole interactions of group IV–VIII element‐containing molecules in tetrahedral geometry with Lewis bases were comparatively scrutinized. The FSiF3, OPF3, NSF3, FClO3, and OArO3 molecules were devoted as Lewis acid centers to interact with NH3 and NCH Lewis bases. According to the results, the most significant σ‐hole interactions were ascribed to the FSiF3⋅⋅⋅ and FClO3⋅⋅⋅Lewis base complexes with interaction energy up to –29.74 kcal mol−1 in the case of the FSiF3⋅⋅⋅NH3 complex. Symmetry‐adapted perturbation theory‐based energy decomposition analysis (SAPT‐EDA) demonstrated that the electrostatic energy (Eelst) was the most prevalent force dominating the explored interactions, while the exchange energies exhibited unfavorable contribution. Quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) results emphasized the closed‐shell nature for all the investigated complexes except FSiF3⋅⋅⋅NH3 complex that demonstrated a covalent nature. Crucially, the utilization of the positively‐ and negatively‐directed external electric field (EEF) led to amelioration and debilitation of the strength of the studied interactions, respectively. The present findings provide knowledge essential to further expanded applications in the fields pertinent to materials science and crystal engineering.

The effects of Lewis basicity and acidity on σ-hole interactions were investigated using two sets of carbon-containing complexes. In Set I, the effect of Lewis basicity was studied by substituting the X3/X atom(s) of the NC-C6H2-X3 and NCX Lewis bases (LB) with F, Cl, Br, or I. In Set II, the W-C-F3 and F-C-X3 (where X and W = F, Cl, Br, and I) molecules were utilized as Lewis acid (LA) centers. Concerning the Lewis basicity effect, higher negative interaction energies (Eint) were observed for the F-C-F3∙∙∙NC-C6H2-X3 complexes compared with the F-C-F3∙∙∙NCX analogs. Moreover, significant Eint was recorded for Set I complexes, along with decreasing the electron-withdrawing power of the X3/X atom(s). Among Set I complexes, the highest negative Eint was ascribed to the F-C-F3∙∙∙NC-C6H2-I3 complex with a value of −1.23 kcal/mol. For Set II complexes, Eint values of F-C-X3 bearing complexes were noted within the −1.05 to −2.08 kcal/mol scope, while they ranged from −0.82 to −1.20 kcal/mol for the W-C-F3 analogs. However, Vs,max quantities exhibited higher values in the case of W-C-F3 molecules compared with F-C-X3; preferable negative Eint were ascribed to the F-C-X3 bearing complexes. These findings were delineated as a consequence of the promoted contributions of the X3 substituents. Dispersion forces (Edisp) were identified as the dominant forces for these interactions. The obtained results provide a foundation for fields such as crystal engineering and supramolecular chemistry studies that focus on understanding the characteristics of carbon-bearing complexes.