T-shaped phenol–benzene complexation driven by π-involved noncovalent interactions

Zhou, Panpan; Yang, Xing; Zhou, Da‐Gang; Liu, Shubin

doi:10.1007/s00214-016-1863-3

Cited by 13 publications

(18 citation statements)

References 72 publications

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“…The electrostatic component was more pronounced in the case of m -CF 3 , further supporting the conclusion that electron-withdrawing substituents strengthen T-shaped interactions ( Figure 4 c). Liu et al 73 reported dispersion and electrostatic contributions of 71% and 23%, respectively, to the total attractive energy for the T-shaped benzene–phenol complex. These values are more similar to those we obtained for the m -OCH 3 complex than for the m -CF 3 complex.…”

Section: Resultsmentioning

confidence: 99%

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Physical Mechanisms Governing Substituent Effects on Arene–Arene Interactions in a Protein Milieu

et al. 2020

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Arene–arene interactions play important roles in protein–ligand complex formation. Here, we investigate the characteristics of arene–arene interactions between small organic molecules and aromatic amino acids in protein interiors. The study is based on X-ray crystallographic data and quantum mechanical calculations using the enzyme acetylcholinesterase and selected inhibitory ligands as a model system. It is shown that the arene substituents of the inhibitors dictate the strength of the interaction and the geometry of the resulting complexes. Importantly, the calculated interaction energies correlate well with the measured inhibitor potency. Non-hydrogen substituents strengthened all interaction types in the protein milieu, in keeping with results for benzene dimer model systems. The interaction energies were dispersion-dominated, but substituents that induced local dipole moments increased the electrostatic contribution and thus yielded more strongly bound complexes. These findings provide fundamental insights into the physical mechanisms governing arene–arene interactions in the protein milieu and thus into molecular recognition between proteins and small molecules.

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Section: Resultsmentioning

confidence: 99%

“…In the equivalent interaction between phenol and benzene, the contributions of dispersion, electrostatics, and induction were 55–62%, 29–32%, and 9–13%, respectively, indicating a more dispersion-dominated interaction. 73 …”

Section: Resultsmentioning

confidence: 99%

Physical Mechanisms Governing Substituent Effects on Arene–Arene Interactions in a Protein Milieu

et al. 2020

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“…For example, com- DFT calculations led to a consistent mechanism for the title reaction (Step I) and the optimized geometries reveal that the transition state of the Au I complexes reacting with EtSH exhibits trigonal planar configuration, in accordance with previous studies on bis-NHC Au I complexes and cysteine-thiols. [27] In the case of the BzImi series, a trigonal reaction intermediate I is also identified, which can then easily progress towards the final Bzi-Au I -SEt product.…”

Section: Fret Dna Melting Assaymentioning

confidence: 98%

Exploring the Reactivity and Biological Effects of Heteroleptic N‐Heterocyclic Carbene Gold(I)‐Alkynyl Complexes

et al. 2020

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With the aim to explore the effects of different organometallic ligands on the reactivity and biological properties of a series of twelve heteroleptic AuI complexes, of general formula [Au(NHC)(alkynyl)] (NHC = benzimidazolylidene or 1,3‐dihydroimidazolylidene) were synthesized and characterized by 1H and 13C NMR and elemental analysis, and in some cases also by X‐ray diffraction. The compounds were all stable in H2O/DMSO as established by NMR spectroscopy, while they could react with model thiols (EtSH) in the presence of water to undergo ligand‐substitution reactions. 1H NMR experiments showed that dissociation of the more labile alkynyl ligand was possible for all compounds, while in the case of the benzimidazolylidene series also dissociation of the NHC ligand could be observed. DFT calculations suggest that, depending on the steric hindrance exerted by both the NHC wingtip groups and the alkynyl substituents, the reaction can proceed either via a π‐stabilized intermediate or with the alkynyl ligand remaining purely σ‐coordinated to the AuI center until completely dissociated. The most stable compounds in PBS buffer (pH 7.4), as assessed by UV‐Visible spectrophotometry, were further investigated for their ability to stabilize G4 DNA by FRET DNA melting assay, showing only moderate activity. Moreover, two derivatives were tested in vitro for their anticancer activities in three different human cancer cell lines and showed cytotoxicity in the low micromolar range.

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“…On the theoretical side, Banerjee and Chakraborty examined with the aid DFT computations the complexes of fluorosubstituted phenols with benzene. Zhou et al analyzed in detail the various geometries that can potentially result from the interaction between phenol and benzene.…”

Section: Introductionmentioning

confidence: 99%

Hyperconjugative effects in π‐hydrogen bonding: Theory and experiment

et al. 2017

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Density functional theory computations with the B3LYP/6-311++G(2df,2p) method and IR spectroscopy are employed in investigating the properties of twenty π-hydrogen bonded complexes between substituted phenols and hexamethylbenzene. All complexes possess T-shaped structures. The methyl hyperconjugative effects on interactions energies and OH stretching frequencies are estimated via comparisons with previously reported theoretical and experimental results for analogous phenol complexes with benzene. The theoretical computations provide excellent quantitative predictions of the OH stretching frequency shifts (Δν ) resulting from the hydrogen bonding. The Δν shifts in the hexamethylbenzene complexes are approximately twice as large as the corresponding shifts for the benzene complexes. Hirshfeld charges, electrostatic potential at nuclei values, and molecular electrostatic potential maps are employed in gaining insights into the mechanisms of methyl hyperconjugative effects on complex formation. © 2017 Wiley Periodicals, Inc.

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T-shaped phenol–benzene complexation driven by π-involved noncovalent interactions

Cited by 13 publications

References 72 publications

Physical Mechanisms Governing Substituent Effects on Arene–Arene Interactions in a Protein Milieu

Physical Mechanisms Governing Substituent Effects on Arene–Arene Interactions in a Protein Milieu

Exploring the Reactivity and Biological Effects of Heteroleptic N‐Heterocyclic Carbene Gold(I)‐Alkynyl Complexes

Hyperconjugative effects in π‐hydrogen bonding: Theory and experiment

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