Probing chiral solute-water hydrogen bonding networks by chirality transfer effects: A vibrational circular dichroism study of glycidol in water

Yang, Guochun; Xu, Yunjie

doi:10.1063/1.3116582

Cited by 58 publications

(74 citation statements)

References 64 publications

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“…Although challenging, quantum chemical predictions for clusters, or solute–DMSO complexes, are to be considered when DMSO solvent is used for experimental measurements. The same comment applies for other hydrogen bonding solvents as well, and studies on solute–solvent clusters are becoming more common in recent years . A recent review by Tomasi and coworkers can be consulted for further insights on modeling the solvent influence.…”

Section: Resultsmentioning

confidence: 96%

Molecular Structure Determination Using Chiroptical Spectroscopy: Where We May Go Wrong?

Polavarapu

2012

Chirality

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Chiroptical spectroscopy is being widely used for determining the three-dimensional molecular structures (i.e., absolute configurations and conformations) of chiral molecules. The general procedure used with any of the chiroptical spectroscopic methods is to analyze the experimental data using corresponding quantum chemical predictions. Such analysis involves multiple steps, including consideration of conformations, solvent effects, electronic transitions, stereoisomers, and experimental artifacts, each of which possesses certain limitations. These limitations, when not recognized or properly taken into account, may lead to incorrect conclusions. This review emphasizes on selected examples that illustrate the potential limitations in utilizing the chiroptical spectroscopic methods. The examples used include hibiscus acid dimethylester, hibiscus acid disodium salt, 3,3'-diphenyl-[2,2'-binaphthalene]-1,1'-diol, tartaric acid esters, and 6,6'-dibromo-[1,1'-binaphthalene]-2,2'-diol.

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Section: Resultsmentioning

confidence: 96%

Molecular Structure Determination Using Chiroptical Spectroscopy: Where We May Go Wrong?

Polavarapu

2012

Chirality

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“…For some of the low-intensity modes even larger intensity changes can be found. Previous studies 34 showed that for measurements in a CHCl 3 solution the use of solvation models was found to yield Phys. Chem.…”

Section: Discussionmentioning

confidence: 98%

Effects of strong and weak hydrogen bond formation on VCD spectra: a case study of 2-chloropropionic acid

Góbi

Vass

Magyarfalvi

et al. 2011

Phys. Chem. Chem. Phys.

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The vibrational circular dichroism (VCD) spectrum of S-(-) and R-(+)-2-chloropropionic acid is thoroughly analyzed. Besides the VCD spectrum of the monomer, the dimers (stabilized by strong hydrogen bonds) and the 2-chloropropionic acid-CHCl(3) complexes (stabilized by a weak hydrogen bond) are studied both experimentally (in solution and in low-temperature Ar matrix) and by quantum chemical computations. It is shown that dimer formation drastically changes, and even weak complex formation can also substantially affect the overall shape of the VCD spectrum. The present and previous results can be generalized for the practice of absolute configuration determination of carboxylic acids by VCD spectroscopy. For these measurements, if bulky groups do not block dimer formation, comparison of the computed spectra of the dimers with the experimental spectra recorded in relatively concentrated (∼0.1 mol dm(-3)) solutions is suggested. Our study also shows that due to the stabilization of monomers and/or the formation of weak complexes, the VCD spectrum recorded in CHCl(3) is more complex and, like in the present case, can have a lower intensity than that of the spectrum recorded in CCl(4). Therefore, if solubility allows, CCl(4) is a much preferred solvent over CHCl(3).

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“…One main goal is to illustrate that VCD and ROA, especially induced solvent VCD features, offer the unique opportunity to differentiate water molecules which form long‐lived direct contacts with the chiral solute from those in the bulk water environment. For example, the induced water VCD signatures at the water bending vibrational region were observed experimentally,,,, and such induced chirality VCD features are due exclusively to the water molecules which are part of the chiral solute‐water n complexes. A second goal is to evaluate the utility of the recently proposed “ clusters‐in‐a‐liquid ” solvation model .…”

Section: Introductionmentioning

confidence: 94%

IR, Raman, and Vibrational Optical Activity Spectra of Methyl Glycidate in Chloroform and Water: The Clusters‐in‐a‐liquid Solvation Model

et al. 2018

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Solvent effects, in particular those involving water as the solvent, are of significant interest to the chemistry and physics communities. IR, vibrational circular dichroism (VCD), Raman, and Raman optical activity (ROA) spectra of methyl glycidate in two very different solvents, namely CCl and water, have been measured experimentally and simulated theoretically. The observed spectra in CCl could be well modelled using the polarizable continuum model for the solvent, whereas the situation is much different in water. The experimental VCD spectrum of methyl glycidate in water reveals strong induced VCD signatures in the water bending region, indicating the presence of the relatively long-lived methyl glycidate-water complexes. We applied the clusters-in-a-liquid approach to identify the dominant methyl glycidate-water complexes which are the long-lived species responsible for all the spectra observed in water. We examined the influences of solvent dielectric environment and the hydrogen-bonding interactions on the conformational distribution of methyl glycidate. The geometry optimizations, frequency calculations, IR, VCD, Raman and ROA intensity calculations were performed at the B3LYP/6-311++G(2d,p) and aug-cc-pVTZ levels of theory with D3BJ dispersion correction. It is particularly satisfying to note that the clusters-in-a-liquid approach has captured all main experimental features in IR, VCD, Raman and ROA spectra of methyl glycidate in water.

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Probing chiral solute-water hydrogen bonding networks by chirality transfer effects: A vibrational circular dichroism study of glycidol in water

Cited by 58 publications

References 64 publications

Molecular Structure Determination Using Chiroptical Spectroscopy: Where We May Go Wrong?

Molecular Structure Determination Using Chiroptical Spectroscopy: Where We May Go Wrong?

Effects of strong and weak hydrogen bond formation on VCD spectra: a case study of 2-chloropropionic acid

IR, Raman, and Vibrational Optical Activity Spectra of Methyl Glycidate in Chloroform and Water: The Clusters‐in‐a‐liquid Solvation Model

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