π-hole interactions of group III–VI elements with π-systems and Lewis bases: a comparative study

Rady, Al‐shimaa S. M.; Soliman, Mahmoud E. S.; Moustafa, Mahmoud; El-Mageed, H. R. Abd; Moussa, Nayra A. M.

doi:10.1007/s11224-021-01817-8

Cited by 12 publications

(7 citation statements)

References 64 publications

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“…Understanding noncovalent forces have been intensively grown in recent years due to their indispensable roles in versatile fields, including supramolecular chemistry, molecular recognition, and materials science. − Their role is also assumptive in biochemical processes, − reinforcing the connections between receptors and ligands that expedite protein transport and enzymatic catalysis. , More recent attention has been drawn among the scientific community toward giving a profound insight into the characterization of σ-hole interactions as one of the most predominant noncovalent interactions. The σ-hole concept was earlier announced − with a view for defining halogen-bonding phenomena, , then extended to include an immense family of noncovalent interactions where the group IV–VI elements interact as Lewis acid centers. − The σ-hole interactions’ occurrence was primarily ascribed to the existence of an area with lesser electron density compared to the surroundings and directly posed along the extension of the σ-bond.…”

Section: Introductionmentioning

confidence: 99%

Effect of External Electric Field on Tetrel Bonding Interactions in (FTF₃···FH) Complexes (T = C, Si, Ge, and Sn)

et al. 2021

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A quantum chemical study was accomplished on the σ-hole interactions of the barely explored group IV elements, for the first time, in the absence and presence of the positively and negatively directed external electric field (EEF). The analyses of molecular electrostatic potential addressed the occurrence of the σ-hole on all the inspected tetrel atoms, confirming their salient versatility to engage in σ-hole interactions. MP2 energetic findings disclosed the occurrence of favorable σ-hole interactions within the tetrel bonding complexes. The tetrel bonding interactions became stronger in the order of C < Si < Ge < Sn for F–T–F3···FH complexes with the largest interaction energy amounting to −19.43 kcal/mol for the optimized F–Sn–F3···FH complex under the influence of +0.020 au EEF. The interaction energy conspicuously evolved by boosting the magnitude of the positively directed EEF value and declining the negatively directed EEF one. The decomposition analysis for the interaction energies was also executed in terms of symmetry-adapted perturbation theory, illuminating the dominant electrostatic contribution to all the studied complexes’ interactions except carbon-based interactions controlled by dispersion forces. The outcomes that emerged from the current work reported significantly how the direction and strength of the EEF affect the tetrel-bonding interactions, leading to further improvements in the forthcoming studies of supramolecular chemistry and materials science.

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Section: Introductionmentioning

confidence: 99%

Effect of External Electric Field on Tetrel Bonding Interactions in (FTF₃···FH) Complexes (T = C, Si, Ge, and Sn)

et al. 2021

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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%

“…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%

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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π-hole interactions of group III–VI elements with π-systems and Lewis bases: a comparative study

Cited by 12 publications

References 64 publications

Effect of External Electric Field on Tetrel Bonding Interactions in (FTF₃···FH) Complexes (T = C, Si, Ge, and Sn)

Effect of External Electric Field on Tetrel Bonding Interactions in (FTF₃···FH) Complexes (T = C, Si, Ge, and Sn)

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

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

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π-hole interactions of group III–VI elements with π-systems and Lewis bases: a comparative study

Cited by 12 publications

References 64 publications

Effect of External Electric Field on Tetrel Bonding Interactions in (FTF3···FH) Complexes (T = C, Si, Ge, and Sn)

Effect of External Electric Field on Tetrel Bonding Interactions in (FTF3···FH) Complexes (T = C, Si, Ge, and Sn)

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

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

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Product

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Effect of External Electric Field on Tetrel Bonding Interactions in (FTF₃···FH) Complexes (T = C, Si, Ge, and Sn)

Effect of External Electric Field on Tetrel Bonding Interactions in (FTF₃···FH) Complexes (T = C, Si, Ge, and Sn)