The effect of fluorine substitution in alcohol–amine complexes

Hansen, Anne S.; Du, Lin; Kjaergaard, Henrik G.

doi:10.1039/c4cp02500h

Cited by 62 publications

(98 citation statements)

References 60 publications

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“…[14][15][16][17][18][19][20][21][22] With this method, equilibrium constants of complex formation are determined from the definition of the equilibrium constant…”

Section: Introductionmentioning

confidence: 99%

The effect of large amplitude motions on the vibrational intensities in hydrogen bonded complexes

Mackeprang

Hänninen

Halonen

et al. 2015

The Journal of Chemical Physics

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We have developed a model to calculate accurately the intensity of the hydrogen bonded XH-stretching vibrational transition in hydrogen bonded complexes. In the Local Mode Perturbation Theory (LMPT) model, the unperturbed system is described by a local mode (LM) model, which is perturbed by the intermolecular modes of the hydrogen bonded system that couple with the intramolecular vibrations of the donor unit through the potential energy surface. We have applied the model to three complexes containing water as the donor unit and different acceptor units, providing a series of increasing complex binding energy: H2O⋯N2, H2O⋯H2O, and H2O⋯NH3. Results obtained by the LMPT model are presented and compared with calculated results obtained by other vibrational models and with previous results from gas-phase and helium-droplet experiments. We find that the LMPT model reduces the oscillator strengths of the fundamental hydrogen bonded OH-stretching transition relative to the simpler LM model.

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“…[14][15][16][17][18][19][20][21][22] With this method, equilibrium constants of complex formation are determined from the definition of the equilibrium constant…”

Section: Introductionmentioning

confidence: 99%

The effect of large amplitude motions on the vibrational intensities in hydrogen bonded complexes

Mackeprang

Hänninen

Halonen

et al. 2015

The Journal of Chemical Physics

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“…[5][6][7][8] In the present work, we consider OH-Y (where Y = N, O, P, S) hydrogen bonds, which have been the focus of a number of gas phase room temperature vibrational spectroscopy studies by some of the authors over the past decade. [9][10][11][12][13] The OH-N hydrogen bond, the strongest of the four, was first detected in the 1960's in the gas phase at room temperature, with large OH-stretching redshifts of ∼300 cm −1 for the complexes between methanol (MeOH) and dimethylamine (DMA) / trimethylamine (TMA). 9,12,14 In contrast, the OH-O, OH-P and OH-S hydrogen bonds are similar and exhibit more modest OH-stretching redshifts of 103-140 cm −1 .…”

mentioning

confidence: 99%

“…[9][10][11][12][13] The OH-N hydrogen bond, the strongest of the four, was first detected in the 1960's in the gas phase at room temperature, with large OH-stretching redshifts of ∼300 cm −1 for the complexes between methanol (MeOH) and dimethylamine (DMA) / trimethylamine (TMA). 9,12,14 In contrast, the OH-O, OH-P and OH-S hydrogen bonds are similar and exhibit more modest OH-stretching redshifts of 103-140 cm −1 . [10][11][12][13]15 Consequently, fewer investigations of these hydrogen bonds exist compared to those of the OH-N hydrogen bond, and at room temperature in the gas phase only limited studies are available.…”

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confidence: 99%

“…It is expected that this will result in OH-N hydrogen bonds of intermediate strength, complementing the existing literature for strong OH-N hydrogen bonds, 9,14,28 and for the weaker OH-O, OH-P and OH-S hydrogen bonds. [10][11][12][13] Three different OH donor molecules are considered, and we have recorded gas phase room temperature vibrational spectra of the methanol-pyridine, ethanol-pyridine and 2,2,2-trifluoroethanol-pyridine complexes. Collectively, this provides gas phase room temperature OH-stretching vibrational spectra for a total of 15 different complexes recorded under similar if not identical experimental conditions.…”

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confidence: 99%

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Kinetic Energy Density as a Predictor of Hydrogen-Bonded OH-Stretching Frequencies

et al. 2017

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This work considers the nature of the intermolecular hydrogen bond in a series of 15 different complexes with OH donor groups and N, O, P, or S acceptor atoms. To complement the existing literature, room-temperature gas-phase vibrational spectra of the methanol-pyridine, ethanol-pyridine, and 2,2,2-trifluoroethanol-pyridine complexes were recorded. These complexes were chosen, as they exhibit hydrogen bonds of intermediate strength as compared to previous investigations that involved strong or weak hydrogen bonds. Non Covalent Interactions (NCI) theory was used to calculate various properties of the intermolecular hydrogen bonds, which were compared to the experimental OH-stretching vibrational red shifts. We find that the experimental OH-stretching red shifts correlate strongly with the kinetic energy density integrated within the reduced density gradient volume that describes a hydrogen bond [G(s)]. Given that vibrational red shifts are commonly used as a metric of the strength of a hydrogen bond, this suggests that G(s) could be used as a predictor of hydrogen bonding strength.

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“…Although small amount of the TFE-TFE dimer exists in the spectra of the mixture, the inuence was minimized by subtracting the contribution of the dimer from the mixture spectra. [29][30][31][32] The spectra in the OH-stretching region obtained with the 20 cm path length cell are very weak (Fig. S3 in ESI †).…”

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Weak hydrogen bonding competition between O–H⋯π and O–H⋯Cl

et al. 2017

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The weak intermolecular interaction between 2,2,2-trifluoroethanol (TFE) and 3-chloro-2-methyl-1-propene (CMP) has been investigated by gas phase FTIR spectroscopy and DFT calculations. CMP offers two hydrogen bond docking sites to the hydrogen bond donor: the chlorine atom (O-H/Cl) and the C]C p electron system (O-H/p). DFT calculations suggest that MeOH approaches CMP in five different orientations. The structural, energetic, and spectroscopic parameters of the most stable structures in each orientation were studied, and their binding energies range from À25.5 to À19.5 kJ mol À1. The docking to the p system is at least 1 kJ mol À1 more favored than the docking to the chlorine atom. The equilibrium constant for complexation (2.3 Â 10 À2 ) was determined from the experimental and calculated intensity of the OH-stretching transition. The Gibbs free energy of formation was found to be 9.3 kJ mol À1. The nature of the non-covalent interaction was analyzed with the atoms in molecules (AIM) method.

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The effect of fluorine substitution in alcohol–amine complexes

Abstract: The effect of fluorine substitution on the hydrogen bond strength in alcohol–amine molecular complexes was investigated, with a combination of vapour phase infrared and near infrared spectroscopy and theoretical calculations.

Cited by 62 publications

References 60 publications

The effect of large amplitude motions on the vibrational intensities in hydrogen bonded complexes

The effect of large amplitude motions on the vibrational intensities in hydrogen bonded complexes

Kinetic Energy Density as a Predictor of Hydrogen-Bonded OH-Stretching Frequencies

Weak hydrogen bonding competition between O–H⋯π and O–H⋯Cl

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