New Way for Probing Bond Strength

Klein, Johanna; Khartabil, Hassan; Boisson, Jean-Charles; Contreras‐García, Julia; Piquemal, Jean‐Philip; Hénon, Éric

doi:10.1021/acs.jpca.9b09845

Cited by 183 publications

(231 citation statements)

References 45 publications

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“…[ 70 ] The “atom pair δg index” can also be interpreted as the tendency of electrons to be shared between two interacting atoms. [ 71 ] Thus, to reach a qualitative insight over the XB NCI between monomers, we also employed Multiwfn to evaluate values of δg I , δg N (as atom δg indices), δg I / N (as atom pair δg index) and

{δg}_{BCP}^{IGM}

and, corresponding values are collected in Table 10. Note, however, that

{δg}_{BCP}^{IGM}

denotes total value of δg IGM computed at the BCP of I … N XB while those of δg I , δg N , and δg I / N indicate, respectively, contribution of I atom from IBZ monomer and N atom from HCN monomer as well as that of I/N atoms pair within the total value of δg IGM between two interacting monomers.…”

Section: Resultsmentioning

confidence: 99%

Exploring influence of fluorine substitution on the strength and nature of halogen bond between iodobenzene and hydrogen cyanide

Naghani

Emamian

Zare

2021

J of Physical Organic Chem

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In the present study, the intermolecular I … N halogen bond (XB) interaction between iodobenzene (IBZ) and its fluorinated derivatives (as Lewis acids LA 1 through LA 20) with HCN (as Lewis base LB) is theoretically explored to shed light on the electronic nature and strength of the mentioned non-covalent interaction (NCI). The hydrogen atoms of phenyl ring in IBZ were substituted by fluorine atom to probe different impacts of this atom. Such a substitution is paid attention from the number as well as the position of fluorine atoms points of view. Our analyses reveal that this XB interaction whose interaction energy spans a narrow range between 1.0 and 3.0 kcalÁmol −1 should be classified as a weak NCI. The symmetry-adapted perturbation theory (SAPT) analysis evidences that the I … N XB in the investigated binary complexes (BCs) is mainly dominated by electrostatic and dispersion interactions, and, in the meantime, induction interactions can safely be ignored. Among the many I … N XB descriptors, V s,max , which corresponds to the most positive value of electrostatic potential computed for the iodine atom in LAs, plays a key role. Indeed, such an easily and rapidly computable quantity (V s,max ) allows a sufficiently accurate prediction of interaction energy together with SAPT-derived components analysis to become feasible by a simple inclusion of V s,max value within the numerous explored estimators. Although the strength of I … N XB interaction in the studied BCs is increased by an increase in the number of fluorine substituent, the position of fluorine atom cannot significantly alter the strength of the mentioned interaction.

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{δg}_{BCP}^{IGM}

and, corresponding values are collected in Table 10. Note, however, that

{δg}_{BCP}^{IGM}

Section: Resultsmentioning

confidence: 99%

Exploring influence of fluorine substitution on the strength and nature of halogen bond between iodobenzene and hydrogen cyanide

Naghani

Emamian

Zare

2021

J of Physical Organic Chem

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“… 65 On that topic, the IGMPlot technique has also recently developed and provides intrinsic bond strength index (IBSI), a numerical evaluation of the interaction between atoms. 66 − 68 …”

Section: Introductionmentioning

confidence: 99%

Evaluation of Electron Density Shifts in Noncovalent Interactions

et al. 2021

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In the present paper, we report the quantitative evaluation of the electron density shift (EDS) maps within different complexes. Values associated with the total EDS maps exhibited good correlation with different quantities such as interaction energies, E int , intermolecular distances, bond critical points, and LMOEDA energy decomposition terms. Besides, EDS maps at different cutoffs were also evaluated and related with the interaction energies values. Finally, EDS maps and their corresponding values are found to correlate with E int within systems with cooperative effects. To our knowledge, this is the first time that the EDS has been quanitatively evaluated.

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“…The sign(λ 2 )ρ b (r) function mapped on the δg inter isosurface and the 2D plot of the δg inter descriptor against sign(λ 2 )ρ b (r) are shown in Figure 6 and Figures S5–S7 . The calculated intrinsic bond strength index (IGMH-IBSI) [ 50 ], which is related to the bond strength (or, more precisely, to the local stretching force constant), falls in the range of 0.007–0.011 and it was slightly higher for TIPA compared to TCPA and TBPA ( Table 5 ). IGMH analysis and IGMH-IBSI values provided us a more quantitative assessment of the main interactions that clearly allow the characterization of the C–X···O interactions as typical weak HaBs.…”

Section: Resultsmentioning

confidence: 99%

Comparative Structural Study of Three Tetrahalophthalic Anhydrides: Recognition of X···O(anhydride) Halogen Bond and πh···O(anhydride) Interaction

et al. 2021

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Structures of three tetrahalophthalic anhydrides (TXPA: halogen = Cl (TCPA), Br (TBPA), I (TIPA)) were studied by X-ray diffraction, and several types of halogen bonds (HaB) and lone pair···π-hole (lp···πh) contacts were revealed in their structures. HaBs involving the central oxygen atom of anhydride group (further X···O(anhydride) were recognized in the structures of TCPA and TBPA. In contrast, for the O(anhydride) atom of TIPA, only interactions with the π system (π-hole) of the anhydride ring (further lp(O)···πh) were observed. Computational studies by a number of theoretical methods (molecular electrostatic potentials, the quantum theory of atoms in molecules, the independent gradient model, natural bond orbital analyses, the electron density difference, and symmetry-adapted perturbation theory) demonstrated that the X···O(anhydride) contacts in TCPA and TBPA and lp(O)···πh in TIPA are caused by the packing effect. The supramolecular architecture of isostructural TCPA and TBPA was mainly affected by X···O(acyl) and X···X HaBs, and, for TIPA, the main contribution provided I···I HaBs.

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New Way for Probing Bond Strength

Cited by 183 publications

References 45 publications

Exploring influence of fluorine substitution on the strength and nature of halogen bond between iodobenzene and hydrogen cyanide

Exploring influence of fluorine substitution on the strength and nature of halogen bond between iodobenzene and hydrogen cyanide

Evaluation of Electron Density Shifts in Noncovalent Interactions

Comparative Structural Study of Three Tetrahalophthalic Anhydrides: Recognition of X···O(anhydride) Halogen Bond and πh···O(anhydride) Interaction

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