CHAPTER 1. Modern Computational Approaches to Understanding Interactions of Aromatics

Lewis, Michael; Bagwill, Christina; Hardebeck, Laura K. E.; Wireduaah, Selina

doi:10.1039/9781782626626-00001

Cited by 5 publications

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“…46 However, there are very few reports investigating the correlation between cation-π binding energies and Hammett substituent constants compared with arene-arene interactions. 47 Dougherty and coworkers appear to be the first researchers to suggest a possible relationship between cation-π binding and Hammett substituent constants. 48 Jiang and co-workers also found excellent correlation between the binding enthalpies and the total Hammett parameter, σ Total .…”

Section: Correlation Between Hammett Constant and Aromaticity With Bi...mentioning

confidence: 99%

Effect of substituent and solvent on cation–π interactions in benzene and borazine: a computational study

et al. 2014

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A DFT and ab initio quantum chemical study has been carried out at different theoretical levels to delve into the role of the cation-π interaction within the main group metal cations (Li(+), Na(+) and K(+)), substituted benzene and borazine. The effects of electron withdrawing and electron donating groups on these non-covalent forces of interaction were also studied. The excellent correlation between Hammett constants and binding energy values indicates that the cation-π interaction is influenced by both inductive and resonance effects. Electron donating groups (EDG) such as -CH3 and -NH2 attached to benzene at the 1, 3 and 5 position and the three boron atoms of borazine were found to strengthen these interactions, while electron withdrawing groups (EWG) such as -NO2 did the reverse. These results were further substantiated by topological analysis using the quantum theory of atoms in molecules (QTAIM). The polarized continuum model (PCM) and the discrete solvation model were used to elucidate the effect of solvation on the cation-π interaction. The size of the cations and the nature of the substituents were found to influence the enthalpy and binding energy of the systems (or complex). In the gas phase, the cation-π interaction was found to be exothermic, whereas in the presence of a polar solvent the interaction was highly endothermic. Thermochemical analysis predicts the presence of thermodynamic driving forces for borazine and benzene substituted with EDG. DFT based reactivity descriptors, such as global hardness (η), chemical potential (μ) and the electrophilicity index (ω) were used to elucidate the effect of the substituent on the reactivity of the cation-π complexes.

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Section: Correlation Between Hammett Constant and Aromaticity With Bi...mentioning

confidence: 99%

Effect of substituent and solvent on cation–π interactions in benzene and borazine: a computational study

et al. 2014

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“…Strong face-to-face contacts are characterized by arene-arene distances of typically 3.7 ± 0.3 Å. [64][65][66] Para-chloroacetophenone exemplifies a donor-acceptor substituted benzene and its crystals feature an arene stacking distance of 4.01 Å (CCDC number: 248149). 67 We cast the topological analysis in terms of double T-contacts Q, T, R, and U as an explanatory device.…”

Section: Crystengcomm Papermentioning

confidence: 99%

Crystal environment induced symmetry reduction (CEISR): deep analysis of para-chloroacetophenone azine and generalization

et al. 2023

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“…[26,[40][41][42] With respect to molecular interactions, the donor proton of the OH group can a priori easily establish an H-bonding (À OH) with the carbonyl site of the PBLG side-chains, while the aromatic and acetylenic substituents can provide π-π interactions (or even π-stacking) with the terminal aromatic ring of the polymer. [43][44][45] To qualitatively evaluate their respective interactions with the polymer side-chain, STD-NMR experiments are performed using identical experimental conditions for the sample preparation. Thus, the polarity of the co-solvent (CD 2 Cl 2 ), ratios of PBLG/co-solvent (w PBLG /w co-solv. )…”

Section: Chemphyschemmentioning

confidence: 99%

Anisotropic ¹H STD‐NMR Spectroscopy: Exploration of Enantiomer‐Polypeptide Interactions in Chiral Oriented Environments

2022

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We explore and report for the first time the use of 1 H saturation transfer difference NMR experiments (STD-NMR) in weakly aligning chiral anisotropic media to identify the hydrogen sites of enantiomers of small chiral molecules interacting with the side-chain of poly-γ-benzyl-l-glutamate (PBLG), a helically chiral polypeptide polymer. The first experimental results obtained on three model mono-stereogenic compounds outcomes are highly promising and demonstrate the possibility to track down possible differences of spatial position of enantiomers at the vicinity of the polymer side-chain. Anisotropic STD experiments appear to be well suited for rapid screening of chiral analytes that bind favorably to orienting polymeric systems, while providing new insights into the mechanism of enantio-discrimination without resorting to the time-consuming determination of molecular order parameters.

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CHAPTER 1. Modern Computational Approaches to Understanding Interactions of Aromatics

Cited by 5 publications

References 0 publications

Effect of substituent and solvent on cation–π interactions in benzene and borazine: a computational study

Effect of substituent and solvent on cation–π interactions in benzene and borazine: a computational study

Crystal environment induced symmetry reduction (CEISR): deep analysis of para-chloroacetophenone azine and generalization

Anisotropic ¹H STD‐NMR Spectroscopy: Exploration of Enantiomer‐Polypeptide Interactions in Chiral Oriented Environments

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CHAPTER 1. Modern Computational Approaches to Understanding Interactions of Aromatics

Cited by 5 publications

References 0 publications

Effect of substituent and solvent on cation–π interactions in benzene and borazine: a computational study

Effect of substituent and solvent on cation–π interactions in benzene and borazine: a computational study

Crystal environment induced symmetry reduction (CEISR): deep analysis of para-chloroacetophenone azine and generalization

Anisotropic 1H STD‐NMR Spectroscopy: Exploration of Enantiomer‐Polypeptide Interactions in Chiral Oriented Environments

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Anisotropic ¹H STD‐NMR Spectroscopy: Exploration of Enantiomer‐Polypeptide Interactions in Chiral Oriented Environments