1H and 19F NMR chemical shifts for hydrogen bond strength determination: Correlations between experimental and computed values

Dalvit, Claudio; Veronesi, Marina; Vulpetti, Anna

doi:10.1016/j.jmro.2022.100070

Cited by 7 publications

(4 citation statements)

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“…The 1 H, 13 C and 15 N SSNMR chemical shifts are well known to be quite sensitive to protonic transfer, in particular for the heteronuclei ( 13 C and 15 N) in carboxylic and pyridinic moieties involved in the resulting hydrogen bonds [ 37 ]. The presence of hydrogen bonds in the crystals was assessed by 1 H MAS spectra; indeed, in general, all hydrogen-bonded 1 H chemical shifts appear to be higher for shorter distances between heavy atoms (i.e., stronger hydrogen bonds) and vice versa, in agreement with the literature [ 37 , 38 , 39 ]. All chemical shifts ( 1 H, 13 C and 15 N) are reported in detail in the Supplementary Materials (Tables S2–S4) while the comparisons between chemical shifts and distances between heavy atoms are reported in Table 1 .…”

Section: Resultssupporting

confidence: 86%

“…In the 1 H MAS spectrum, the hydrogen-bond region (above 10 ppm) is characterised by one signal at 14.7 ppm (H1) and another one at 20.4 ppm (H8); the former is consistent with a pyridinium proton involved in a hydrogen bond of intermediate strength, the latter with the presence of a COOH group involved in very strong hydrogen bonds, usually an intramolecular interaction [ 37 , 38 , 39 ]; this agrees with both the intramolecular hydrogen bond between carboxylic groups present in the experimental crystal structure of the system and the short distance between heavy atoms (see Table 1 ).…”

Section: Resultsmentioning

confidence: 99%

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Zwitterionic or Not? Fast and Reliable Structure Determination by Combining Crystal Structure Prediction and Solid-State NMR

et al. 2023

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When it comes to crystal structure determination, computational approaches such as Crystal Structure Prediction (CSP) have gained more and more attention since they offer some insight on how atoms and molecules are packed in the solid state, starting from only very basic information without diffraction data. Furthermore, it is well known that the coupling of CSP with solid-state NMR (SSNMR) greatly enhances the performance and the accuracy of the predictive method, leading to the so-called CSP-NMR crystallography (CSP-NMRX). In this paper, we present the successful application of CSP-NMRX to determine the crystal structure of three structural isomers of pyridine dicarboxylic acid, namely quinolinic, dipicolinic and dinicotinic acids, which can be in a zwitterionic form, or not, in the solid state. In a first step, mono- and bidimensional SSNMR spectra, i.e., 1H Magic-Angle Spinning (MAS), 13C and 15N Cross Polarisation Magic-Angle Spinning (CPMAS), 1H Double Quantum (DQ) MAS, 1H-13C HETeronuclear CORrelation (HETCOR), were used to determine the correct molecular structure (i.e., zwitterionic or not) and the local molecular arrangement; at the end, the RMSEs between experimental and computed 1H and 13C chemical shifts allowed the selection of the correct predicted structure for each system. Interestingly, while quinolinic and dipicolinic acids are zwitterionic and non-zwitterionic, respectively, in the solid state, dinicotinic acid exhibits in its crystal structure a “zwitterionic-non-zwitterionic continuum state” in which the proton is shared between the carboxylic moiety and the pyridinic nitrogen. Very refined SSNMR experiments were carried out, i.e., 14N-1H Phase-Modulated (PM) pulse and Rotational-Echo Saturation-Pulse Double-Resonance (RESPDOR), to provide an accurate N–H distance value confirming the hybrid nature of the molecule. The CSP-NMRX method showed a remarkable match between the selected structures and the experimental ones. The correct molecular input provided by SSNMR reduced the number of CSP calculations to be performed, leading to different predicted structures, while RMSEs provided an independent parameter with respect to the computed energy for the selection of the best candidate.

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Section: Resultssupporting

confidence: 86%

Section: Resultsmentioning

confidence: 99%

Zwitterionic or Not? Fast and Reliable Structure Determination by Combining Crystal Structure Prediction and Solid-State NMR

et al. 2023

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“…It has long been recognized that proton chemical shifts are affected by hydrogen bonding. − In the case of solitary water, the OH-stretching frequency is exquisitely sensitive to hydrogen bonding, and it has been shown to provide a convenient measure of solvent hydrogen-bond accepting ability (“β”). , Throughout this work, we use shifts in the average frequency of the OH-stretching band of solitary water, Δν OH = ν OH gas – ν OH solution , as the primary measure of the strength of water-solvent electrostatic interactions. In Figure a, we compare water–benzene chemical shift differences, Δδ W  – (δ W – δ B ), to OH stretching frequencies in a variety of dipolar (blue) and ionic (red) solvents.…”

Section: Resultsmentioning

confidence: 99%

Do Electrostatics Control the Diffusive Dynamics of Solitary Water? NMR and MD Studies of Water Translation and Rotation in Dipolar and Ionic Solvents

Mukherjee,

Palchowdhury,

Maroncelli

2024

J. Phys. Chem. B

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NMR-based measurements of the diffusion coefficients and rotation times of solitary water and benzene at 300 K are reported in a diverse collection of 13 conventional organic solvents and 10 imidazolium ionic liquids. Proton chemical shifts of water are found to be correlated to water OH-stretching frequencies, confirming the importance of electrostatic interactions in these shifts. However, the influence of magnetic interactions in aromatic solvents renders chemical shifts a less reliable indicator of electrostatics. Diffusion coefficients (D B ) and rotational correlation times (τ B ) of benzene in the solvents examined are accurately described as functions of viscosity (η) by D B ∝ η −0.81 and τ B ∝ η 0.64 . Literature values of D B and τ B in alkane and normal alcohols, which were not included among the solvents studied here, are systematically faster than predicted by these correlations, indicating that factors beyond solvent viscosity play a role in determining the friction on benzene. In contrast to benzene, water diffusion and rotation are poorly described in terms of viscosity alone, even in the dipolar and ionic solvents measured here. The present data and the substantial literature data already available on dilute water diffusion show a systematic dependence of D W on solvent polarity among isoviscous solvents. The aspect of solvent polarity most relevant to water dynamics is the ability of a solvent to accept hydrogen bonds from water, as conveniently quantified by the frequency of water's OH stretching band, Δν OH . The friction on translation, ζ tr = k B T/D W , and rotation, ζ rot = k B Tτ W , are both well correlated by functions of the form ζ(η, Δν OH ) = a 1 η a 2 exp (a 3 Δν OH ), where the a i are adjustable parameters. Molecular dynamics simulations reveal a strong coupling between electrostatic and nonelectrostatic water-solvent interactions, which makes it impossible to dissect the friction on water into additive dielectric and hydrodynamic components. Simulations also provide a tentative explanation for the unusual form of the correlating function ζ(η, Δν OH ), at least in the case of ζ rot .

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“…3,4 However, there is a gap of knowledge on nonconventional intramolecular H-bond interactions that needs to be assessed in order to fully understand the role this kind of interaction plays in the conformational stability and preference of molecules, and also to enhance the conformational design protocols in drug discovery, 5 for example. Furthermore, the rapid ascension of fluorinated molecules in the pharmaceutical field [6][7][8][9][10][11][12][13] highlights the demand for a better under-standing of the effects caused by the insertion of fluorine atom(s) on organic molecules, their stereoelectronic effects and the influence of hydrogen bonding [14][15][16][17][18][19][20][21] on their conformational preference.…”

Section: Introductionmentioning

confidence: 99%

Molecular dynamics and NMR reveal the coexistence of H-bond-assisted and through-space J_FH coupling in fluorinated amino alcohols

Chiari,

Batista,

Viesser

et al. 2024

Org. Biomol. Chem.

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1H and 19F NMR chemical shifts for hydrogen bond strength determination: Correlations between experimental and computed values

Cited by 7 publications

References 68 publications

Zwitterionic or Not? Fast and Reliable Structure Determination by Combining Crystal Structure Prediction and Solid-State NMR

Zwitterionic or Not? Fast and Reliable Structure Determination by Combining Crystal Structure Prediction and Solid-State NMR

Do Electrostatics Control the Diffusive Dynamics of Solitary Water? NMR and MD Studies of Water Translation and Rotation in Dipolar and Ionic Solvents

Molecular dynamics and NMR reveal the coexistence of H-bond-assisted and through-space J_FH coupling in fluorinated amino alcohols

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1H and 19F NMR chemical shifts for hydrogen bond strength determination: Correlations between experimental and computed values

Cited by 7 publications

References 68 publications

Zwitterionic or Not? Fast and Reliable Structure Determination by Combining Crystal Structure Prediction and Solid-State NMR

Zwitterionic or Not? Fast and Reliable Structure Determination by Combining Crystal Structure Prediction and Solid-State NMR

Do Electrostatics Control the Diffusive Dynamics of Solitary Water? NMR and MD Studies of Water Translation and Rotation in Dipolar and Ionic Solvents

Molecular dynamics and NMR reveal the coexistence of H-bond-assisted and through-space JFH coupling in fluorinated amino alcohols

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Molecular dynamics and NMR reveal the coexistence of H-bond-assisted and through-space J_FH coupling in fluorinated amino alcohols