A comparative investigation for the versatility of sp 2-hybridized trivalent triel-containing molecules to engage in � π-hole interactions with Lewis base, Lewis acid, σ-hole-containing molecules, and lp-hole-containing molecules was dwelled using quantum mechanical calculations. According to the results, it was found that the À π-hole interactions were more favorable than the + π-hole ones, with larger negative interaction energies and shorter intermolecular distance. + π-hole interactions with lp-hole-containing molecules were observed with larger substantial interaction energies than Lewis acids, and σ-hole-containing molecules varied from-0.65 to-5.18 kcal/mol. Quantum theory of atoms in molecules and noncovalent interaction index analyses revealed the noncovalent nature for � π-hole interactions. As well, symmetry-adapted perturbation theory-based energy decomposition analysis affirmed that electrostatic and dispersion forces controlled the À π-hole interactions, whereas the + π-hole analogs were dominated by dispersion forces only. These findings will be of advantage to the forthcoming studies in the materials and supramolecular chemistry.
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 efficacy of pure and aluminum (Al)-doped boron nitride nanocarriers (B12N12 and AlB11N12) in adsorbing Chlormethine (CM), an anti-cancer drug, was comparatively dissected by means of the density functional theory method. The CM∙∙∙B12N12 and ∙∙∙AlB11N12 complexes were studied within two configurations, A and B, in which the adsorption process occurred via N∙∙∙ and Cl∙∙∙B/Al interactions, respectively. The electrostatic potential affirmations confirmed the opulent ability of the studied nanocarriers to engage in delivering CM via two prominent electrophilic sites (B and Al). Furthermore, the adsorption process within the CM∙∙∙AlB11N12 complexes was noticed to be more favorable compared to that within the CM∙∙∙B12N12 analog and showed interaction and adsorption energy values up to –59.68 and −52.40 kcal/mol, respectively, for configuration A. Symmetry-adapted perturbation theory results indicated that electrostatic forces were dominant in the adsorption process. Notably, the adsorption of CM over B12N12 and AlB11N12 nanocarriers exhibited predominant changes in their electronic properties. An elemental alteration was also revealed for the softness and hardness of B12N12 and AlB11N12 nanocarriers before and following the CM adsorption. Spontaneity and exothermic nature were obviously observed for the studied complexes and confirmed by the negative values of thermodynamic parameters. In line with energetic manifestation, Gibbs free energy and enthalpy change were drastically increased by the Al doping process, with values raised to –37.15 and –50.14 kcal/mol, respectively, for configuration A of the CM∙∙∙AlB11N12 complex. Conspicuous enhancement was noticed for the adsorption process in the water phase more than that in the gas phase and confirmed by the negative values of the solvation energy up to −53.50 kcal/mol for configuration A of the CM∙∙∙AlB11N12 complex. The obtained outcomes would be the linchpin for the future utilization of boron nitride as a nanocarrier.
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