Subtle differences in the hydrogen bonding of alcohol to divalent oxygen and sulfur

Du, Lin; Tang, Shanshan; Hansen, Anne S.; Frandsen, Benjamin N.; Maroun, Zeina; Kjaergaard, Henrik G.

doi:10.1016/j.cplett.2016.11.045

Cited by 38 publications

(65 citation statements)

References 43 publications

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“…As seen from Figs. 1 and S1 , only gauche- conformer was found in optimized structures of the complexes in the present study, which is in agreement with former studies 13 , 18 , 19 . However, there is still controversy about the reason why the gauche- conformer is more stable.…”

Section: Resultssupporting

confidence: 93%

“…For example, equilibrium constants of 0.13, 0.3, 0.26 were obtained for TFE−TMP, TFE–ethylene oxide, TFE–dimethylether, respectively 17 – 19 . However, these K eq values are about an order of magnitude smaller than those of TFE−TMA ( K eq = 3.5) and TFE−DMA ( K eq = 3.6) complexes 16 , while about an order of magnitude larger when compared with that of TFE−dimethylsulfide ( K eq = 0.052) 18 complex. The K eq values listed above suggest moderate thermostability of the complexes formed between TFE and the select heterocyclic compounds in the present study.…”

Section: Resultsmentioning

confidence: 78%

“…Hydrogen bonded MeOH−TMA and MeOH−DMA complexes were detected with gas phase FTIR spectroscopy 48 , and the values calculated for the complexes were 11.4 and 10.6 kJ mol −1 at the B3LYP/aug-cc-pVTZ level of theory, corresponding to BE s of −19.7 and −20.8 kJ mol −1 , respectively. The formation of hydrogen bonded TFE−dimethylether and TFE−dimethylsulfide were identified in the gas phase with FTIR spectroscopy 18 , the values of the complexes were found to be 4.2 and 8.1 kJ mol −1 at the B3LYP-D3/aug-cc-pVTZ level of theory, and the BE s for the complexes were −31.3 and −28.1 kJ mol −1 , accordingly. The possibility of complexation between two molecules is relevant to .…”

Section: Resultsmentioning

confidence: 99%

“…In a similar study, using same hydrogen bond donors but the trimethylphosphine (TMP) as acceptor, the TFE–TMP complex was found to be most stable among the TFE/EtOH/MeOH–TMP complexes 17 , indicating that the presence of the CF 3 group facilitates the formation of strong hydrogen bond. Hydrogen bonding interactions between TFE and dimethylether or dimethylsulfide have been investigated with FTIR and density functional theory (DFT) calculations, by which the strengths of O−H···O and O−H···S hydrogen bonds were found to be very similar 18 . Using similar methods, another study of complexes formed between TFE and ethylene oxide or ethylene sulfide also identified that O−H···O and O−H···S hydrogen bonds have comparable strength 19 .…”

Section: Introductionmentioning

confidence: 99%

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The Influence of the Position of the Double Bond and Ring Size on the Stability of Hydrogen Bonded Complexes

Cheng

Tang

Tsona

et al. 2017

Sci Rep

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To study the influence of the position of the double bond and ring size on the stability of hydrogen bonded complexes, the 1:1 complexes formed between 2,2,2-trifluoroethanol (TFE) and three heterocyclic compounds including 2,3-dihydrofuran (2,3-DHF), 2,5-dihydrofuran (2,5-DHF) and 3,4-dihydropyran (3,4-DHP) were investigated systematically. The formation of hydrogen bonded TFE−2,3-DHF, TFE−2,5-DHF and TFE−3,4-DHP complexes were identified by gas phase FTIR spectroscopy at room temperature, and the OH-stretching fundamental transition of TFE was red shifted upon complexation. The competition between the O atom and π-electrons bonding sites within the complexes was studied, and the O−H···π type hydrogen bond was found to be less stable than the O−H···O in all three cases. The observed red shifts of the OH-stretching fundamental transitions in the complexes were attributed to the formation of O−H···O hydrogen bond. Equilibrium constants of the complexation reactions were determined from measured and calculated OH-stretching fundamental intensities. Both theoretical calculations and experimental results reveal that the hydrogen bond strengths in the complexes follow the sequence: TFE−2,5-DHF > TFE−2,3-DHF ≈ TFE−3,4-DHP, thus the position of the double bond exerts significantly larger influence than ring size on the stability of the selected hydrogen bonded complexes.Atmospheric nanometer sized clusters play an important role in the formation and growth of aerosol particles. These clusters are usually stabilized by hydrogen bonding interactions [1][2][3][4][5] . Investigation of hydrogen bonded complexes formed between atmospheric relevant molecules is important in understanding the characteristics of particles at the molecular level. According to previous researches, hydrogen bonded complexes can be formed among a number of molecules, such as alcohols, amines and aromatic compounds [5][6][7][8] . Alcohols have the ability to form hydrogen bonded complexes either as hydrogen bond donor or hydrogen bond acceptor through the H atom or the O atom of the hydroxyl group, respectively. A particular case of atmospherically relevant alcohol in complex formation is the 2,2,2-trifluoroethanol (TFE), one of the widely used fluorinated alcohols that is available on a large commercial scale. It has been used in many reactions as solvent, cosolvent, catalyst, and it is also important for the preparation of many pharmaceuticals and other chemicals [9][10][11][12] . Increased production and use of TFE will lead to an increase of its emission into the atmosphere. The electron withdrawing CF 3 group present in TFE enhances its acidity and makes it a strong proton donor 13,14 . Considering the close correlation between hydrogen bonded clusters and new particles formation, it is necessary to study the interactions of TFE with compounds present in the atmosphere.Hydrogen bonding interactions between TFE and various atmospheric components have been explored by many studies, both theoretically and experimentally. Hydrogen bonded complexes...

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Section: Resultssupporting

confidence: 93%

Section: Resultsmentioning

confidence: 78%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The Influence of the Position of the Double Bond and Ring Size on the Stability of Hydrogen Bonded Complexes

Cheng

Tang

Tsona

et al. 2017

Sci Rep

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“…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. 10,[16][17][18][19][20][21][22][23][24][25][26][27] In the present work, we consider three examples of OH-N hydrogen bonds in complexes that involve pyridine, which is a weaker N based acceptor molecule than DMA or TMA.…”

mentioning

confidence: 99%

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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Spectroscopic Determination of Hydrogen Bond Energies

Goswami¹,

Arunan²

2022

Spectroscopy and Computation of Hydrogen‐Bonded Systems

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Subtle differences in the hydrogen bonding of alcohol to divalent oxygen and sulfur

Cited by 38 publications

References 43 publications

The Influence of the Position of the Double Bond and Ring Size on the Stability of Hydrogen Bonded Complexes

The Influence of the Position of the Double Bond and Ring Size on the Stability of Hydrogen Bonded Complexes

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

Spectroscopic Determination of Hydrogen Bond Energies

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