Interactions of hypervalent IF and XeFO molecules σ-hole site with Lewis bases and anions: a comparative study.

Interactions of hypervalent IF and XeFO molecules within the square pyramidal geometry σ-hole site with Lewis bases (LB = NH and NCH) and anions (X = F, Cl, Br, and I) were comparatively investigated using methods. The energetic features outlined remarkable interaction ( ) and binding ( ) energies for all complexes aligned from -5.65 to -91.02 kcal mol and from -5.53 to -65.89 kcal mol, respectively. More negative and values were demonstrated for XeFO⋯LB complexes, compared to IF⋯LB complexes, along with nominal deformation energies for all complexes. Turning to IF⋯ and XeFO⋯X complexes, demonstrated the proficiency of the latter complexes, which was in synchronic with the claims. On the contrary, IF⋯X complexes demonstrated higher negative values in comparison to XeFO⋯X complexes, which may be attributed to the considerable favorable deformation energies relevant to the former complexes rather than the latter candidates. Moreover, the and were disclosed to ameliorate in coincidence with the Lewis basicity strength as follows: IF/XeFO⋯NCH < ⋯NH < ⋯I < ⋯Br < ⋯Cl < ⋯F. Quantum theory of atoms in molecules/noncovalent interactions index observations affirmed that the interactions of IF/XeFO molecules σ-hole site with NH and NCH were characterized with open- and closed-shell nature, respectively, while the IF/XeFO⋯X complexes were characterized with the coordinative covalent nature. Symmetry-adapted perturbation theory results pinpointed the predominance of the inspected interactions with the electrostatic forces. The acquired results will be advantageous for the ubiquitous investigation of understanding the impact of geometrical deformation on the interactions of hypervalent molecules and their applications in diverse fields such as materials science and crystal engineering.