Comparative investigation of ±σ–hole interactions of carbon-containing molecules with Lewis bases, acids and di-halogens

Mahmoud, Amna H. M.; Moussa, Nayra A. M.

doi:10.1007/s11696-020-01187-1

Cited by 18 publications

(34 citation statements)

References 44 publications

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“…The value of the employed PoC to investigate the Chal···PoC distance effect was made equal to the one used in optimization. The strength of the σ-hole and lp hole interactions was estimated in terms of the molecular stabilization energy ( E stablization ) according to the following equation: 12 , 13 , 18 , 34 , 35 …”

Section: Methodsmentioning

confidence: 99%

“…The σ-hole and lp hole interactions will first be investigated from the electrostatic perspective via the point-of-charge (PoC) approach. 12 , 13 , 18 , 34 , 35 In addition, the PoC approach will be utilized to precisely define lp, lp hole, and σ-hole locations. Moreover, the Lewis basicity effect on the strength of the σ-hole and lp hole interactions will be also examined.…”

Section: Introductionmentioning

confidence: 99%

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σ-Hole and Lone-Pair Hole Interactions in Chalcogen-Containing Complexes: A Comparative Study

Telb

2020

ACS Omega

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The potentiality of sp 3 -hybridized chalcogen-containing molecules to participate in lone-pair (lp) hole interactions was reported for the first time. lp hole interactions were characterized and compared to σ-hole ones for OF 2 and SF 2 molecules as a case study . Various quantum mechanical calculations, including molecular electrostatic potential (MEP), maximum positive electrostatic potential ( V s,max ), point of charge (PoC), symmetry-adapted perturbation theory (SAPT), quantum theory of atoms in molecule (QTAIM), and reduced density gradient–noncovalent interaction (RDG-NCI) calculations, were carried out. The more significant findings to emerge from this study are the following: (i) the V s,max calculation was proved to be an unreliable method to determine the precise σ-hole and lp hole locations. (ii) The maximum positive electrostatic potential of the σ hole and lp hole was found to be at the F–Chal···PoC angle (θ) of 180° and at the centroid of XYlp plane, respectively. (iii) Lewis basicity has a significant effect on the strength of σ-hole and lp hole interactions. (iv) The studied molecules more favorably interact with Lewis bases via the σ hole compared to the lp hole, and (v) stabilization of the σ-hole and lp hole interactions stems from the electrostatic and dispersion forces, respectively.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

σ-Hole and Lone-Pair Hole Interactions in Chalcogen-Containing Complexes: A Comparative Study

Telb

2020

ACS Omega

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“…Furthermore, the B⋅⋅⋅PoC distance effect on the given electrostatic interactions was studied through distances ranging from 2.5 Å to 5.0 Å along x‐axis with step size of 0.1 Å and X‐B⋅⋅⋅PoC angle of 90° (see Figure 1). The strength of the π‐hole interaction was estimated in terms of molecular stabilization energy ( E stablization ) according to the following equation: [21,28a, 19a, 17, 19b, 28b]

true E_{s t a b l i z a t i o n} = E_{b o r o n - c o n t a i n i n g m o l e c u l e \cdot \cdot \cdot P o C} - E_{b o r o n - c o n t a i n i n g m o l e c u l e}

…”

Section: Computational Methodologymentioning

confidence: 99%

“…[16] More recently, the À σ-hole and + σ-hole interactions were explored to conceive the potentiality of carbon-containing molecules to interact with negative and positive electrostatic sites, respectively. [17] Comparatively, À σ-hole interactions showed more favorable negative interaction energies than + σhole ones. Parallel to À σ-hole and + σ-hole interactions, À π-hole, and + π-hole analogs have not been elucidated yet.…”

Section: Introductionmentioning

confidence: 93%

“…Along with the π‐hole, the σ‐hole is another remarkable type of electron‐deficient region that enables Group IV–VII elements in the periodic table to interact with Lewis bases forming tetrel, [13] pnicogen, [14] chalcogen, [15] and halogen bonds [16] . More recently, the − σ‐hole and + σ‐hole interactions were explored to conceive the potentiality of carbon‐containing molecules to interact with negative and positive electrostatic sites, respectively [17] . Comparatively, − σ‐hole interactions showed more favorable negative interaction energies than + σ‐hole ones.…”

Section: Introductionmentioning

confidence: 99%

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^±π‐Hole Interactions: A Comparative Investigation Based on Boron‐Containing Molecules

et al. 2020

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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.

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σ‐Hole Interactions of Tetrahedral Group IV–VIII Lewis Acid Centers with Lewis Bases: A Comparative Study

et al. 2021

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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.

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Comparative investigation of ±σ–hole interactions of carbon-containing molecules with Lewis bases, acids and di-halogens

Cited by 18 publications

References 44 publications

σ-Hole and Lone-Pair Hole Interactions in Chalcogen-Containing Complexes: A Comparative Study

σ-Hole and Lone-Pair Hole Interactions in Chalcogen-Containing Complexes: A Comparative Study

^±π‐Hole Interactions: A Comparative Investigation Based on Boron‐Containing Molecules

σ‐Hole Interactions of Tetrahedral Group IV–VIII Lewis Acid Centers with Lewis Bases: A Comparative Study

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