Abstract
In the current study, unexplored type IV halogen⋯halogen interaction was thoroughly elucidated, for the first time, and compared to the well-established types I–III interactions by means of the second-order Møller–Plesset (MP2) method. For this aim, the halobenzene⋯halobenzene homodimers (where halogen = Cl, Br, and I) were designed into four different types, parodying the considered interactions. From the energetic perspective, the preference of scouted homodimers was ascribed to type II interactions (i.e., highest binding energy), whereas the lowest binding energies were discerned in type III interactions. Generally, binding energies of the studied interactions were observed to decline with the decrease in the σ-hole size in the order, C6H5I⋯IC6H5 > C6H5Br⋯BrC6H5 > C6H5Cl⋯ClC6H5 homodimers and the reverse was noticed in the case of type IV interactions. Such peculiar observations were relevant to the ample contributions of negative-belt⋯negative-belt interactions within the C6H5Cl⋯ClC6H5 homodimer. Further, type IV torsional trans → cis interconversion of C6H5X⋯XC6H5 homodimers was investigated to quantify the π⋯π contributions into the total binding energies. Evidently, the energetic features illustrated the amelioration of the considered homodimers (i.e., more negative binding energy) along the prolonged scope of torsional trans → cis interconversion. In turn, these findings outlined the efficiency of the cis configuration over the trans analog. Generally, symmetry-adapted perturbation theory-based energy decomposition analysis (SAPT-EDA) demonstrated the predominance of all the scouted homodimers by the dispersion forces. The obtained results would be beneficial for the omnipresent studies relevant to the applications of halogen bonds in the fields of materials science and crystal engineering.
Highlights
The σ-hole interactions are of growing interest to researchers from various disciplines, owing to their wide applications in catalysis [1], anion recognition [2], biological systems [3,4], crystal materials [5,6], and drug discovery [7]
Four different types of halogen· · · halogen interactions were comparatively scrutinized within the C6H5X· · · XC6H5 homodimers, using a versatile range of quantum mechanical calculations
The occurrence of the σ-hole along the surface of the studied halogen atoms was found to be the common feature within the inspected molecules, as affirmed by molecular electrostatic potential (MEP) maps, which enabled them to behave as potent halogen bond donors
Summary
The σ-hole interactions are of growing interest to researchers from various disciplines, owing to their wide applications in catalysis [1], anion recognition [2], biological systems [3,4], crystal materials [5,6], and drug discovery [7]. The occurrence of such interactions was mainly ascribed to the anisotropic distribution of the electron density on the surfaces of group IV-VII elements [8–13], resulting in the emergence of an electron depletion region coined as “σ-hole” [14,15]. Among σ-hole interactions, the halogen bond encouraged growing attention by dint of its decisive character in protein–ligand binding affinity [16–18], crystal engineering [19–21], and organo-catalysis [22,23]. Versatile computational [24–28] and experimental [29–32] studies were devoted to characterizing halogen bonding interactions. The amphoteric nature of the halogen-containing molecules was thoroughly spotted, and their potentiality to simultaneously interact as a Lewis base and a Lewis acid was widely assessed, in the case of like–like complexes [34–41]
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