R•-hole interactions of group IV-VII radical-containing molecules: A comparative study

Mohamed, Yasmeen A. M.; Elhafez, Heba S. M. Abd; Shehata, Mohammed N. I.; Soliman, Mahmoud E. S.; Ahmed, Muhammad Naeem; El-Mageed, H. R. Abd; Moussa, Nayra A. M.

doi:10.1016/j.jmgm.2021.108097

Cited by 7 publications

(12 citation statements)

References 57 publications

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“…The Point-of-charge (PoC) approach was documented as an informative tool for elucidating the electrostatic inclination of the group III-VIII element-containing molecules to participate in noncovalent interactions [ 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 ]. With the help of the PoC approach, negatively and positively charged points were utilized to parody the nucleophilic and electrophilic effects on the inspected molecular systems, respectively.…”

Section: Resultsmentioning

confidence: 99%

Type I–IV Halogen⋯Halogen Interactions: A Comparative Theoretical Study in Halobenzene⋯Halobenzene Homodimers

Saeed

Shehata

Ahmed

et al. 2022

IJMS

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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.

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Section: Resultsmentioning

confidence: 99%

Type I–IV Halogen⋯Halogen Interactions: A Comparative Theoretical Study in Halobenzene⋯Halobenzene Homodimers

Saeed

Shehata

Ahmed

et al. 2022

IJMS

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“…The PoC approach was recently reported as a trustworthy method to evaluate the σ- [ 17 , 57 ], π- [ 58 , 59 ], lp- [ 60 ], and R • [ 61 ]-hole interactions from an electrostatic perspective. PoC calculations were conducted to inspect the distance impact on NC-C 6 H 2 -X 3 ∙∙∙, NCX∙∙∙, W-C-F 3 ∙∙∙, and F-C-X 3 ∙∙∙PoC systems under the effect of PoC = ±0.50 au.…”

Section: Resultsmentioning

confidence: 99%

Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio Study

Shehata

Rady

Abuelliel

et al. 2022

IJMS

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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.

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Section: Resultsmentioning

confidence: 99%

“…The nucleophilic and electrophilic natures of the chemical systems are accordingly addressed from an electrostatic perspective in terms of molecular stabilization energy . The PoC approach has recently been notarized as a trustworthy method for studying the σ-hole, − lp-hole, π-hole, , and R • -hole interactions from an electrostatic point of view. ,, With the help of the PoC approach, the ability of the PCl 3 molecule to interact with Lewis bases and acids was investigated by employing negative and positive PoCs, respectively. ± σ-Hole and ± lp-hole tests were executed for the optimized PCl 3 molecule under the influence of 0.000, ±0.002, ±0.004, ± 0.006, and ±0.008 au EEF at σ-hole··· and lp-hole···PoC distance in the range of 2.5–6.0 Å with a step size of 0.1 Å using a PoC value of ±0.50 au.…”

Section: Resultsmentioning

confidence: 99%

“…33 The PoC approach has recently been notarized as a trustworthy method for studying the σ-hole, 94−96 lp-hole, 15 π-hole, 97,98 and R • -hole 99 interactions from an electrostatic point of view. 15,99,100 With the help of the PoC approach, the ability of the PCl 3 molecule to interact with Lewis bases and acids was investigated by employing negative and positive PoCs, respectively. With regard to the effect of the EEF strength, the molecular stabilization energy increased with increasing the magnitude of 1).…”

Section: Methodsmentioning

confidence: 99%

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σ-Hole and LP-Hole Interactions of Pnicogen···Pnicogen Homodimers under the External Electric Field Effect: A Quantum Mechanical Study

et al. 2022

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σ-Hole and lone-pair (lp)-hole interactions within σ-hole···σ-hole, σ-hole···lp-hole, and lp-hole···lp-hole configurations were comparatively investigated on the pnicogen···pnicogen homodimers (PCl 3 ) 2 , for the first time, under field-free conditions and the influence of the external electric field (EEF). The electrostatic potential calculations emphasized the impressive versatility of the examined PCl 3 monomers to participate in σ-hole and lp-hole pnicogen interactions. Crucially, the sizes of σ-hole and lp-hole were enlarged under the influence of the positively directed EEF and decreased in the case of reverse direction. Interestingly, the energetic quantities unveiled more favorability of the σ-hole···lp-hole configuration of the pnicogen···pnicogen homodimers, with significant negative interaction energies, than σ-hole···σ-hole and lp-hole···lp-hole configurations. Quantum theory of atoms in molecules and noncovalent interaction index analyses were adopted to elucidate the nature and origin of the considered interactions, ensuring their closed shell nature and the occurrence of attractive forces within the studied homodimers. Symmetry-adapted perturbation theory-based energy decomposition analysis alluded to the dispersion force as the main physical component beyond the occurrence of the examined interactions. The obtained findings would be considered as a fundamental underpinning for forthcoming studies pertinent to chemistry, materials science, and crystal engineering.

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R•-hole interactions of group IV-VII radical-containing molecules: A comparative study

Cited by 7 publications

References 57 publications

Type I–IV Halogen⋯Halogen Interactions: A Comparative Theoretical Study in Halobenzene⋯Halobenzene Homodimers

Type I–IV Halogen⋯Halogen Interactions: A Comparative Theoretical Study in Halobenzene⋯Halobenzene Homodimers

Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio Study

σ-Hole and LP-Hole Interactions of Pnicogen···Pnicogen Homodimers under the External Electric Field Effect: A Quantum Mechanical Study

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