Competition between H···π and H···O Interactions in Furan Heterodimers

Sánchez-García, Elsa; Jansen, Georg

doi:10.1021/jp301710y

Cited by 13 publications

(9 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…All energies are obtained with Gaussian 09, thus the slight discrepancy in energy difference between the conformers to Table 1. type of donor molecule. 32 For acetylene, a He droplet experiment has provided evidence for both isomers 33 and the downshift of the asymmetric CH stretch was found to be slightly larger for p bonding, as also observed in the present methanol investigation. For indole, only the p-bound isomer was observed when docking to furan.…”

Section: Discussionsupporting

confidence: 86%

Subtle solvation behaviour of a biofuel additive: the methanol complex with 2,5-dimethylfuran

Poblotzki

Altnöder

Suhm

2016

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Methanol is shown to engage two nearly equivalent solvation sites in 2,5-dimethylfuran, the electron-rich π cloud and the electron-deficient oxygen site. The latter only wins by a slight margin, thanks to the methyl group undergoing secondary interactions with the ring. These secondary attractions reduce the hydrogen bond-induced OH frequency shift of the OH-O contact, whereas the π cloud allows for a combined action of both binding mechanisms in the OH-π arrangement. In total, the hydrophobic character of 2,5-dimethylfuran is well reflected in the weak pair interactions, as judged by the small solvation shifts. Methanol solvation of 2,3-benzofuran is revisited and shown to be more ambiguous than previously thought, involving competition between five- and six-ring π clouds and the oxygen site for the OH group. The six-ring π cloud is slightly preferred. FTIR spectroscopy in supersonic jets is in systematic agreement with dispersion-corrected harmonic B3LYP and also B2PLYP predictions for these competing furan docking sites. Deuteration of the OH group helps to identify the docking sites because of its attenuated zero-point energy weakening effect on localized hydrogen bonds. Extension to less methylated furans is proposed in the context of a future forecasting competition for the performance of quantum chemical methods for intermolecular interactions.

show abstract

Section: Discussionsupporting

confidence: 86%

Subtle solvation behaviour of a biofuel additive: the methanol complex with 2,5-dimethylfuran

Poblotzki

Altnöder

Suhm

2016

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…An independent calculation involving two furan molecules in the orientation observed in (Ia) yields a BSSE-corrected value of À7.7 kJ mol À1 . These values agree well with the À9.8 kJ mol À1 obtained for an optimized ethyne-furan interaction energy (Sá nchez-García & Jansen, 2012). A similar analysis using the minor contributor to the disorder in (Ia) yields a value of À8.8 kJ mol À1 for the Bz-Fn C-HÁ Á Á interaction, which is in good agrement with the value of À9.4 kJ mol À1 reported for the interaction energy of a 'T-shaped' benzene dimer (Sherrill et al, 2009).…”

Section: Tablesupporting

confidence: 88%

Structure determination of three furan-substituted benzimidazoles and calculation of π–π and C—H...π interaction energies

Geiger

Deck

2014

Acta Crystallogr C

View full text Add to dashboard Cite

The synthesis and structural characterization of 2-(furan-2-yl)-1-(furan-2-ylmethyl)-1H-benzimidazole [C16H12N2O2, (I)], 2-(furan-2-yl)-1-(furan-2-ylmethyl)-1H-benzimidazol-3-ium chloride monohydrate [C16H13N2O2(+)·Cl(-)·H2O, (II)] and the hydrobromide salt 5,6-dimethyl-2-(furan-2-yl)-1-(furan-2-ylmethyl)-1H-benzimidazol-3-ium bromide [C18H17N2O2(+)·Br(-), (III)] are described. Benzimidazole (I) displays two sets of aromatic interactions, each of which involves pairs of molecules in a head-to-tail arrangement. The first, denoted set (Ia), exhibits both intermolecular C-H···π interactions between the 2-(furan-2-yl) (abbreviated as Fn) and 1-(furan-2-ylmethyl) (abbreviated as MeFn) substituents, and π-π interactions involving the Fn substituents between inversion-center-related molecules. The second, denoted set (Ib), involves π-π interactions involving both the benzene ring (Bz) and the imidazole ring (Im) of benzimidazole. Hydrated salt (II) exhibits N-H···OH2···Cl hydrogen bonding that results in chains of molecules parallel to the a axis. There is also a head-to-head aromatic stacking of the protonated benzimidazole cations in which the Bz and Im rings of one molecule interact with the Im and Fn rings of adjacent molecules in the chain. Salt (III) displays N-H···Br hydrogen bonding and π-π interactions involving inversion-center-related benzimidazole rings in a head-to-tail arrangement. In all of the π-π interactions observed, the interacting moieties are shifted with respect to each other along the major molecular axis. Basis set superposition energy-corrected (counterpoise method) interaction energies were calculated for each interaction [DFT, M06-2X/6-31+G(d)] employing atomic coordinates obtained in the crystallographic analyses for heavy atoms and optimized H-atom coordinates. The calculated interaction energies are -43.0, -39.8, -48.5, and -55.0 kJ mol(-1) for (Ia), (Ib), (II), and (III), respectively. For (Ia), the analysis was used to partition the interaction energies into the C-H···π and π-π components, which are 9.4 and 24.1 kJ mol(-1), respectively. Energy-minimized structures were used to determine the optimal interplanar spacing, the slip distance along the major molecular axis, and the slip distance along the minor molecular axis for 2-(furan-2-yl)-1H-benzimidazole.

show abstract

“…ref. [9][10][11][12][13][14] can be expected. The Fujii group 15 investigated clusters of 1-naphthol with methanol, ethanol, tert-butyl alcohol and water using combined IR/UV spectroscopy and assigned exclusively OH-O isomers for all clusters with the hydroxyl moiety of 1-naphthol acting as a hydrogen bond donor.…”

Section: Introductionmentioning

confidence: 93%

Multi-spectroscopic and theoretical analyses on the diphenyl ether–tert-butyl alcohol complex in the electronic ground and electronically excited state

Bernhard

Dietrich

Fatima

et al. 2017

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

a Aromatic ethers such as diphenyl ether (DPE) represent molecules with different docking sites for alcohols leading to competing OH-O and OH-p interactions. In a multi-spectroscopic approach in combination with quantum chemical calculations the complex of DPE with tert-butyl alcohol (t-BuOH) is investigated in the electronic ground state (S 0 ) and the electronically excited state (S 1 ). FTIR, microwave as well as mass-and isomer-selective IR/R2PI spectra are recorded, revealing co-existing OH-O and OH-p isomers in the S 0 state. Surprisingly, they are predicted to be of almost equal stability in contrast to the previously investigated DPE-MeOH complex, where the OH-p structure is preferred by both theory and experiment. The tert-butyl group in t-BuOH allows for a simultaneous optimization of hydrogen-bonding and dispersion interactions, which provides a sensitive meeting point between theory and experiment. In the electronically excited state of DPE-t-BuOH, vibrational spectra could be recorded separately for both isomers using UV/IR/UV spectroscopy. In the S 1 state the same structural binding motifs are obtained as in the S 0 state with the OH-O bond being weakened for the OH-O arrangement and the OH-p interaction being strengthened in the case of the OH-p isomer compared to the S 0 state.

show abstract

Competition between H···π and H···O Interactions in Furan Heterodimers

Cited by 13 publications

References 49 publications

Subtle solvation behaviour of a biofuel additive: the methanol complex with 2,5-dimethylfuran

Subtle solvation behaviour of a biofuel additive: the methanol complex with 2,5-dimethylfuran

Structure determination of three furan-substituted benzimidazoles and calculation of π–π and C—H...π interaction energies

Multi-spectroscopic and theoretical analyses on the diphenyl ether–tert-butyl alcohol complex in the electronic ground and electronically excited state

Contact Info

Product

Resources

About