Hydrogen bonds in quinoline N-oxide derivatives: first-principle molecular dynamics and metadynamics ground state study

Panek, Jarosław J.; Błaziak, Kacper; Jezierska, Aneta

doi:10.1007/s11224-015-0720-7

Cited by 13 publications

(9 citation statements)

References 40 publications

(64 reference statements)

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“…They assigned a feature at 2330 cm −1 to the OH stretching band, but the P(Harm) value is 2877 cm −1 [ 19 ]. The P(Harm) prediction was confirmed by correlation with NMR parameters [ 19 ] and was subsequently supported by the results of an advanced molecular dynamics simulation [ 70 ].…”

Section: Theoretical Predictionsmentioning

confidence: 80%

“…In an analysis of the importance of vibrationally enhanced catalysis, Kamerlin, Mavri, and Warshel [ 66 ] concluded that dynamical effects and tunneling are irrelevant for enzyme catalysis. Car-Parrinello molecular dynamics calculations were also applied by Durlak et al [ 67 , 68 , 69 ] in investigations of the vibrational structure of compounds like nitromalonamide enol ( 4 ) and 2-acetyl-1,8-dihydroxy-3,6-dimethylnaphthalene ( 7 ), and by Panek et al [ 70 ] in a study of intramolecular hydrogen bonds in a series of 8-hydroxyquinoline N -oxide ( 8 ) derivatives.…”

Section: Theoretical Predictionsmentioning

confidence: 99%

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NMR and IR Investigations of Strong Intramolecular Hydrogen Bonds

2017

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For the purpose of this review, strong hydrogen bonds have been defined on the basis of experimental data, such as OH stretching wavenumbers, νOH, and OH chemical shifts, δOH (in the latter case, after correction for ring current effects). Limits for O–H···Y systems are taken as 2800 > νOH > 1800 cm−1, and 19 ppm > δOH > 15 ppm. Recent results as well as an account of theoretical advances are presented for a series of important classes of compounds such as β-diketone enols, β-thioxoketone enols, Mannich bases, proton sponges, quinoline N-oxides and diacid anions. The O···O distance has long been used as a parameter for hydrogen bond strength in O–H···O systems. On a broad scale, a correlation between OH stretching wavenumbers and O···O distances is observed, as demonstrated experimentally as well as theoretically, but for substituted β-diketone enols this correlation is relatively weak.

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Section: Theoretical Predictionsmentioning

confidence: 80%

Section: Theoretical Predictionsmentioning

confidence: 99%

NMR and IR Investigations of Strong Intramolecular Hydrogen Bonds

2017

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“…The presence of this interaction is able to stabilize the geometry of a molecule as well as to change the electron density distribution and further molecular features. The current work is a continuation of our study on N -oxide type compounds on the basis of diverse theoretical approaches. − We have studied previously picolinic acid N -oxide as a small system, nevertheless with complicated spectroscopic features and proton dynamics. Static models were not able to reproduce its features, and the use of Car–Parrinello molecular dynamics enabled us to obtain an accurate picture of the bridged proton delocalization.…”

Section: Introductionmentioning

confidence: 99%

N-oxide Derivatives: Car–Parrinello Molecular Dynamics and Electron Localization Function Study on Intramolecular Hydrogen Bonds

Panek

Jezierska

2018

J. Phys. Chem. A

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First-principle molecular dynamics simulations (CPMD) and electron localization function (ELF) topological analysis were performed for two N-oxides, 2-[( N, N-dimethylamino- N-oxy)methyl]-4,6-dimethylphenol (I) and 5,5'-dibromo-3-[(diethylamino)methyl]-2,2'-biphenol N-oxide (II). Special attention was paid to hydrogen bond dynamics and spectroscopic features. Simulations were carried out in vacuo and in the crystalline phase. It was found that for compound I proton transfer phenomena do not occur spontaneously. An opposite situation was noticed for one of the two intramolecular hydrogen bonds of compound II. The influence of the neighboring molecules (including microsolvation) and the crystal field on the hydrogen bond properties cannot be neglected. Hydrogen bond spectroscopic signatures were quite well reproduced by power spectra of atomic velocity. Metric and spectroscopic theoretical findings were compared with experimental data available, especially in a view of the fact that experimental X-ray diffraction and FT-IR data of compound II indicate strong delocalization of the N-oxide bridge proton. ELF analysis showed that for compound II the N-oxide bridge belongs to the topological category of strong hydrogen bonds with the separate ELF basin for the bridged hydrogen atom.

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“…In the current study, we focused on intra- and intermolecular interactions in two N -oxides: 2-(N,N-dimethylamino-N-oxymethyl)-4,6-dimethylphenyl ( 1 ) [ 43 ] and 5,5’-dibromo-3-diethylaminomethyl-2,2’-biphenol N -oxide ( 2 ) [ 44 ]. N -oxides are interesting objects for experimental and theoretical studies because of their unusual chemical structure, possessing N→O bonds, which is involved in inter- or intramolecular hydrogen bond formation [ 45 , 46 , 47 , 48 , 49 ]. It was showed that the N -oxide group exhibits proton acceptor ability for hydroxyl, carboxyl, amine groups or water molecules.…”

Section: Introductionmentioning

confidence: 99%

Exploring Intra- and Intermolecular Interactions in Selected N-Oxides—The Role of Hydrogen Bonds

et al. 2022

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Intra- and intermolecular interactions have been explored in selected N-oxide derivatives: 2-(N,N-dimethylamino-N-oxymethyl)-4,6-dimethylphenyl (1) and 5,5’-dibromo-3-diethylaminomethyl-2,2’-biphenol N-oxide (2). Both compounds possess intramolecular hydrogen bonding, which is classified as moderate in 1 and strong in 2, and resonance-assisted in both cases. Density Functional Theory (DFT) in its classical formulation as well as Time-Dependent extension (TD-DFT) were employed to study proton transfer phenomena. The simulations were performed in the gas phase and with implicit and explicit solvation models. The obtained structures of the studied N-oxides were compared with experimental data available. The proton reaction path was investigated using scan with an optimization method, and water molecule reorientation in the monohydrate of 1 was found upon the proton scan progress. It was found that spontaneous proton transfer phenomenon cannot occur in the electronic ground state of the compound 1. An opposite situation was noticed for the compound 2. The changes of nucleophilicity and electrophilicity upon the bridged proton migration were analyzed on the basis of Fukui functions in the case of 1. The interaction energy decomposition of dimers and microsolvation models was investigated using Symmetry-Adapted Perturbation Theory (SAPT). The simulations were performed in both phases to introduce polar environment influence on the interaction energies. The SAPT study showed rather minor role of induction in the formation of homodimers. However, it is worth noticing that the same induction term is responsible for the preference of water molecules’ interaction with N-oxide hydrogen bond acceptor atoms in the microsolvation study. The Natural Bond Orbital (NBO) analysis was performed for the complexes with water to investigate the charge flow upon the polar environment introduction. Finally, the TD-DFT was applied for isolated molecules as well as for microsolvation models showing that the presence of solvent affects excited states, especially when the N-oxide acceptor atom is microsolvated.

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Hydrogen bonds in quinoline N-oxide derivatives: first-principle molecular dynamics and metadynamics ground state study

Cited by 13 publications

References 40 publications

NMR and IR Investigations of Strong Intramolecular Hydrogen Bonds

NMR and IR Investigations of Strong Intramolecular Hydrogen Bonds

N-oxide Derivatives: Car–Parrinello Molecular Dynamics and Electron Localization Function Study on Intramolecular Hydrogen Bonds

Exploring Intra- and Intermolecular Interactions in Selected N-Oxides—The Role of Hydrogen Bonds

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