Quantum chemical calculations with the AIM approach applied to the π-interactions between hydrogen chalcogenides and naphthalene

Hayashi, Satoko; Sugibayashi, Yuji; Nakanishi, Warō

doi:10.1039/c6ra04738f

Cited by 7 publications

(4 citation statements)

References 47 publications

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“…QTAIM‐DFA was recently formulated on the basis of QTAIM . The H b ( r c ) parameters are plotted versus H b ( r c )− V b ( r c )/2 [=(ħ 2 /8 m )∇ 2 ρ b ( r c )] at the BCPs in QTAIM‐DFA.…”

Section: Introductionmentioning

confidence: 99%

Intrinsic Dynamic Nature of Neutral Hydrogen Bonds Elucidated with QTAIM Dual Functional Analysis: Role of the Compliance Force Constants and QTAIM‐DFA Parameters in Stability

2018

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The dynamic and static nature of various neutral hydrogen bonds (nHBs) is elucidated with quantum theory of atoms‐in‐molecules dual functional analysis (QTAIM‐DFA). The perturbed structures generated by using the coordinates derived from the compliance force constants (Cij) of internal vibrations are employed for QTAIM‐DFA. The method is called CIV. The dynamic nature of CIV is described as the “intrinsic dynamic nature”, as the coordinates are invariant to the choice of the coordinate system. nHBs are, for example, predicted to be van der Waals (H2Se−✶−HSeH; ✶=bond critical point), t‐HBnc (typical‐HBs with no covalency: HI−✶−HI), t‐HBwc (t‐HBs with covalency: H2C=O−✶−HI), CT‐MC [molecular complex formation through charge transfer (CT): H2C=O−✶−HF], and CT‐TBP (trigonal bipyramidal adduct formation through CT: H3N−✶−HI) in nature. The results with CIV were the same as those with POM in the calculation errors, for which the perturbed structures were generated by partial optimization, and the interaction distances in question were fixed suitably in POM. The highly excellent applicability of CIV for QTAIM‐DFA was demonstrated for the various nHBs, as well as for the standard interactions previously reported. The stability of the HBs, evaluated by ΔE, is well correlated with Cij (ΔE×Cij=constant value of −165.64), and the QTAIM parameters, although a few deviations were detected.

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Section: Introductionmentioning

confidence: 99%

Intrinsic Dynamic Nature of Neutral Hydrogen Bonds Elucidated with QTAIM Dual Functional Analysis: Role of the Compliance Force Constants and QTAIM‐DFA Parameters in Stability

2018

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“…and the Laplacian of electron density, showing alternation in electronic charge, is positive. These characteristics are typical for such interactions [112].…”

Section: Binding and Structural Studiesmentioning

confidence: 86%

Thiourea Organocatalysts as Emerging Chiral Pollutants: En Route to Porphyrin-Based (Chir)Optical Sensing

et al. 2021

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Environmental pollution with chiral organic compounds is an emerging problem requiring innovative sensing methods. Amino-functionalized thioureas, such as 2-(dimethylamino)cyclohexyl-(3,5-bis(trifluoromethyl)phenyl)thiourea (Takemoto’s catalyst), are widely used organocatalysts with virtually unknown environmental safety data. Ecotoxicity studies based on the Vibrio fischeri luminescence inhibition test reveal significant toxicity of Takemoto’s catalyst (EC50 = 7.9 mg/L) and its NH2-substituted analog (EC50 = 7.2–7.4 mg/L). The observed toxic effect was pronounced by the influence of the trifluoromethyl moiety. En route to the porphyrin-based chemosensing of Takemoto-type thioureas, their supramolecular binding to a series of zinc porphyrins was studied with UV-Vis and circular dichroism (CD) spectroscopy, computational analysis and single crystal X-ray diffraction. The association constant values generally increased with the increasing electron-withdrawing properties of the porphyrins and electron-donating ability of the thioureas, a result of the predominant Zn⋯N cation–dipole (Lewis acid–base) interaction. The binding event induced a CD signal in the Soret band region of the porphyrin hosts—a crucial property for chirality sensing of Takemoto-type thioureas.

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“…We recently reported the dynamic and static nature of π-HBs and π-XBs in the coronene π-system (π(C 24 H 12 )) [ 21 , 22 ], together with those in benzene (π(C 6 H 6 )) [ 23 , 24 , 25 ], naphthalene (π(C 10 H 8 )) [ 26 ], and anthracene (π(C 14 H 10 )) [ 27 ]. We have also been very interested in the behavior of π-HBs and π-XBs in distorted π-systems.…”

Section: Introductionmentioning

confidence: 99%

Dynamic and Static Nature of XH-∗-π and YX-∗-π (X = F, Cl, Br, and I; Y = X and F) in the Distorted π-System of Corannulene Elucidated with QTAIM Dual Functional Analysis

et al. 2023

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The dynamic and static nature of the XH-∗-π and YX-∗-π (X = F, Cl, Br, and I; Y = X and F) interactions in the distorted π-system of corannulene (π(C20H10)) is elucidated with a QTAIM dual functional analysis (QTAIM-DFA), where asterisks emphasize the presence of bond critical points (BCPs) on the interactions. The static and dynamic nature originates from the data of the fully optimized and perturbed structures, respectively, in QTAIM-DFA. On the convex side, H in F–H-∗-π(C20H10) and each X in Y–X-∗-π(C20H10) join to C of the central five-membered ring in π(C20H10) through a bond path (BP), while each H in X–H-∗-π(C20H10) does so to the midpoint of C=C in the central five-membered ring for X = Cl, Br, or I. On the concave side, each X in F–X-∗-π(C20H10) also joins to C of the central five-membered ring with a BP for X = H, Cl, Br, and I; however, the interactions in other adducts are more complex than those on the convex side. Both H and X in X–H-∗-π(C20H10) (X = Cl and Br) and both Fs in F–F-∗-π(C20H10) connect to the three C atoms in each central five-membered ring (with three BPs). Two, three, and five BPs were detected for the Cl–Cl, I–H, Br–Br, and I–I adducts, where some BPs do not stay on the central five-membered ring in π(C20H10). The interactions are predicted to have a vdW to CT-MC nature. The interactions on the concave side seem weaker than those on the convex side for X–H-∗-π(C20H10), whereas the inverse trend is observed for Y–X-∗-π(C20H10) as a whole. The nature of the interactions in the π(C20H10) adducts of the convex and concave sides is examined in more detail, employing the adducts with X–H and F–X placed on their molecular axis together with the π(C24H12) and π(C6H6) adducts.

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Quantum chemical calculations with the AIM approach applied to the π-interactions between hydrogen chalcogenides and naphthalene

Abstract: The nature of π-interactions in (EH2)n––π(C10H8) (n = 1 and 2: E = O, S, Se and Te) is elucidated with QTAIM-DFA. They have the character of the vdW-nature of the pure-CS interactions, except for HHTe––π(C10H8), which seems stronger than others.

Cited by 7 publications

References 47 publications

Intrinsic Dynamic Nature of Neutral Hydrogen Bonds Elucidated with QTAIM Dual Functional Analysis: Role of the Compliance Force Constants and QTAIM‐DFA Parameters in Stability

Intrinsic Dynamic Nature of Neutral Hydrogen Bonds Elucidated with QTAIM Dual Functional Analysis: Role of the Compliance Force Constants and QTAIM‐DFA Parameters in Stability

Thiourea Organocatalysts as Emerging Chiral Pollutants: En Route to Porphyrin-Based (Chir)Optical Sensing

Dynamic and Static Nature of XH-∗-π and YX-∗-π (X = F, Cl, Br, and I; Y = X and F) in the Distorted π-System of Corannulene Elucidated with QTAIM Dual Functional Analysis

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Quantum chemical calculations with the AIM approach applied to the π-interactions between hydrogen chalcogenides and naphthalene

Abstract: The nature of π-interactions in (EH2)n–*–π(C10H8) (n = 1 and 2: E = O, S, Se and Te) is elucidated with QTAIM-DFA. They have the character of the vdW-nature of the pure-CS interactions, except for HHTe–*–π(C10H8), which seems stronger than others.

Cited by 7 publications

References 47 publications

Intrinsic Dynamic Nature of Neutral Hydrogen Bonds Elucidated with QTAIM Dual Functional Analysis: Role of the Compliance Force Constants and QTAIM‐DFA Parameters in Stability

Intrinsic Dynamic Nature of Neutral Hydrogen Bonds Elucidated with QTAIM Dual Functional Analysis: Role of the Compliance Force Constants and QTAIM‐DFA Parameters in Stability

Thiourea Organocatalysts as Emerging Chiral Pollutants: En Route to Porphyrin-Based (Chir)Optical Sensing

Dynamic and Static Nature of XH-∗-π and YX-∗-π (X = F, Cl, Br, and I; Y = X and F) in the Distorted π-System of Corannulene Elucidated with QTAIM Dual Functional Analysis

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Abstract: The nature of π-interactions in (EH2)n––π(C10H8) (n = 1 and 2: E = O, S, Se and Te) is elucidated with QTAIM-DFA. They have the character of the vdW-nature of the pure-CS interactions, except for HHTe––π(C10H8), which seems stronger than others.