Dimethyl Sulfoxide Complexes Detected at Ambient Conditions

Hansen, Anne S.; Kjaergaard, Henrik G.

doi:10.1021/acs.jpca.7b06102

Cited by 7 publications

(6 citation statements)

References 78 publications

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“…The close values of complexation energies of TFA···DMK and TFA···DEE indicate similar proton acceptor abilities of acetone and ether. The same conclusion was derived previously from the gas phase spectral properties and calculations of complexes of methanol with acetone and dimethyl ether …”

Section: Resultssupporting

confidence: 86%

IR Spectra of Hydrogen-Bonded Complexes of Trifluoroacetic Acid with Acetone and Diethyl Ether in the Gas Phase. Interaction between CH and OH Stretching Vibrations

Asfin

2019

J. Phys. Chem. A

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The spectra of complexes of trifluoroacetic acid (TFA) with acetone and diethyl ether (DEE) and their perdeuterated isotopologues were extracted from the spectra of the mixture of the compounds recorded at room temperature. The ν(OH) bands of the complexes with protiated and deuterated acetone notably differ from each other, whereas these ν(OH) bands are practically not affected by the deuteration of DEE. An assumption about the interaction of CH and OH groups in the (CH 3 )−CO•••HO fragment is made. According to density functional theory calculations, complexes of TFA with both acetone and DEE have a cyclic structure with one strong O•••HO hydrogen bond and one weak CH•••O bond. The structural, spectroscopic, and electronic properties indicate an essential role of weak bonds in the total complexation energy of the systems studied.

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Section: Resultssupporting

confidence: 86%

IR Spectra of Hydrogen-Bonded Complexes of Trifluoroacetic Acid with Acetone and Diethyl Ether in the Gas Phase. Interaction between CH and OH Stretching Vibrations

Asfin

2019

J. Phys. Chem. A

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“…These intramolecular modes are also coupled with two intermolecular modes, donor rock and donor twist modes, via Rayleigh–Schrödinger perturbation theory. , The potential energy surfaces used for the LMPT calculations, were also CP corrected. The LMPT intensities have been estimated to be within about 35% of the experimental values for the water dimer, where experimental intensities exist. − …”

Section: Methodsmentioning

confidence: 61%

Room Temperature Gibbs Energies of Hydrogen-Bonded Alcohol Dimethylselenide Complexes

2019

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A number of hydrogen-bonded complexes, formed between an alcohol donor and dimethylselenide, have been detected experimentally, at room temperature in the gas phase using FTIR spectroscopy. The Gibbs energy of complex formation has been determined from the measured integrated absorbance of the hydrogen-bonded OH stretching band and the calculated oscillator strength of the associated transition. The OH stretching frequency and Gibbs energy of the selenium hydrogen-bonded complexes are compared to those found in complexes with the same donor molecule and either dimethylether (O) or dimethylsulfide (S) as the acceptor molecule. For a given donor, we found a similar OH stretching frequency in the complexes for each of the three acceptors O, S, and Se. However, the Gibbs energies were found to be less positive (i.e., stronger bound) for the dimethylether complexes (OH•O), as compared to the dimethylsulfide (OH•S) and dimethylselenide (OH•Se) complexes, with the latter two having comparable Gibbs energies.

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“…It might, however, be observed in suitable room temperature gas phase complexes. 47,48 An analogous resonance has not yet been assigned for alcohols as ketone solvents instead of water, 49 but a different resonance was observed slightly below 3500 cm −1 for a double methanol solvate of acetone. 15 This confirms that the robust HOH bend, rather than a variable HOR bend in alcohols, is an essential ingredient to the universality of the resonance position.…”

mentioning

confidence: 91%

A Rather Universal Vibrational Resonance in 1:1 Hydrates of Carbonyl Compounds

Fischer

Wagner

Gottschalk

et al. 2020

J. Phys. Chem. Lett.

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When the lower frequency OH stretching fundamental of a water molecule is shifted to the 3500 cm −1 spectral range by the solvation of a carbonyl compound, in this case a ketone, its infrared intensity is shared with a dark state. It is shown by chemical and isotope substitution for more than a dozen systems that the location of this resonance is remarkably substitution-independent. Harmonic and anharmonic model calculations support its assignment to a combination of the water bending overtone and in-plane water libration. This previously unrecognized intramolecular−intermolecular coupling in single solvent water has a strength of 7−10 cm −1 . It may have been sporadically observed before in a few other carbonyl compounds such as amides, without any previous exploration of its potential universality. The resulting generic picosecond energy redistribution channel for aqueous solutions may represent a slow counterpart and doorway model of what happens on a subpicosecond time scale when the hydrogen bonds become stronger, such as in carboxylic acid dimers or protonated water clusters.

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Dimethyl Sulfoxide Complexes Detected at Ambient Conditions

Cited by 7 publications

References 78 publications

IR Spectra of Hydrogen-Bonded Complexes of Trifluoroacetic Acid with Acetone and Diethyl Ether in the Gas Phase. Interaction between CH and OH Stretching Vibrations

IR Spectra of Hydrogen-Bonded Complexes of Trifluoroacetic Acid with Acetone and Diethyl Ether in the Gas Phase. Interaction between CH and OH Stretching Vibrations

Room Temperature Gibbs Energies of Hydrogen-Bonded Alcohol Dimethylselenide Complexes

A Rather Universal Vibrational Resonance in 1:1 Hydrates of Carbonyl Compounds

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