<sup>±</sup>π‐Hole Interactions: A Comparative Investigation Based on Boron‐Containing Molecules

Rady, Al‐shimaa S. M.; Al‐Fahemi, Jabir H.; Telb, Ebtisam M. Z.; Ahmed, Saleh A.; Shawky, Ahmed M.; Moussa, Nayra A. M.

doi:10.1002/slct.202003231

Cited by 14 publications

(10 citation statements)

References 58 publications

(58 reference statements)

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“…Parallel to the π- and lone-pair (lp)-hole tests, − ± σ-hole tests were advanced to critically examine the potentiality of σ-atom-containing molecules to engage in noncovalent interactions with the help of PoC approach. − In ± σ-hole tests, the correlation between the T/X···PoC distance and the molecular stabilization energy was established in the presence of ±0.50 au PoC (see the Computational Methodology section for more details). Figure displays the molecular stabilization energy curves for X-T-X 3 ···PoC systems that were generated in a T/X···PoC distance range of 2.5–5.5 Å. Molecular stabilization energies for the studied X-T-X 3 ···PoC systems in the presence of ±0.50 au PoC at T/X···PoC distance of 2.5 Å are collected in Table .…”

Section: Resultsmentioning

confidence: 99%

On the Potentiality of X-T-X₃ Compounds (T = C, Si, and Ge, and X = F, Cl, and Br) as Tetrel- and Halogen-Bond Donors

et al. 2021

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The versatility of the X-T-X3 compounds (where T = C, Si, and Ge, and X = F, Cl, and Br) to participate in tetrel- and halogen-bonding interactions was settled out, at the MP2/aug-cc-pVTZ level of theory, within a series of configurations for (X-T-X3)2 homodimers. The electrostatic potential computations ensured the remarkable ability of the investigated X-T-X3 monomers to participate in σ-hole halogen and tetrel interactions. The energetic findings significantly unveil the favorability of the tetrel···tetrel directional configuration with considerable negative binding energies over tetrel···halogen, type III halogen···halogen, and type II halogen···halogen analogs. Quantum theory of atoms in molecules and noncovalent interaction analyses were accomplished to disclose the nature of the tetrel- and halogen-bonding interactions within designed configurations, giving good correlations between the total electron densities and binding energies. Further insight into the binding energy physical meanings was invoked through using symmetry-adapted perturbation theory-based energy decomposition analysis, featuring the dispersion term as the most prominent force beyond the examined interactions. The theoretical results were supported by versatile crystal structures which were characterized by the same type of interactions. Presumably, the obtained findings would be considered as a solid underpinning for future supramolecular chemistry, materials science, and crystal engineering studies, as well as a fundamental linchpin for a better understanding of the biological activities of chemicals.

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Section: Resultsmentioning

confidence: 99%

On the Potentiality of X-T-X₃ Compounds (T = C, Si, and Ge, and X = F, Cl, and Br) as Tetrel- and Halogen-Bond Donors

et al. 2021

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

Cited by 14 publications

References 58 publications

On the Potentiality of X-T-X₃ Compounds (T = C, Si, and Ge, and X = F, Cl, and Br) as Tetrel- and Halogen-Bond Donors

On the Potentiality of X-T-X₃ Compounds (T = C, Si, and Ge, and X = F, Cl, and Br) as Tetrel- and Halogen-Bond Donors

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

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

Cited by 14 publications

References 58 publications

On the Potentiality of X-T-X3 Compounds (T = C, Si, and Ge, and X = F, Cl, and Br) as Tetrel- and Halogen-Bond Donors

On the Potentiality of X-T-X3 Compounds (T = C, Si, and Ge, and X = F, Cl, and Br) as Tetrel- and Halogen-Bond Donors

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

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

On the Potentiality of X-T-X₃ Compounds (T = C, Si, and Ge, and X = F, Cl, and Br) as Tetrel- and Halogen-Bond Donors

On the Potentiality of X-T-X₃ Compounds (T = C, Si, and Ge, and X = F, Cl, and Br) as Tetrel- and Halogen-Bond Donors

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