Subtle solvation behaviour of a biofuel additive: the methanol complex with 2,5-dimethylfuran
2016 | journal article. A publication of Göttingen
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Subtle solvation behaviour of a biofuel additive: the methanol complex with 2,5-dimethylfuran
Poblotzki, A.; Altnöder, J. & Suhm, M. A. (2016)
Physical Chemistry Chemical Physics, 18(39) pp. 27265-27271. DOI: https://doi.org/10.1039/c6cp05413g
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Details
- Authors
- Poblotzki, Anja; Altnöder, Jonas; Suhm, Martin A.
- Abstract
- Methanol is shown to engage two nearly equivalent solvation sites in 2,5-dimethylfuran, the electronrich p 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 p cloud allows for a combined action of both binding mechanisms in the OH–p 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 p clouds and the oxygen site for the OH group. The six-ring p 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.
- Issue Date
- 2016
- Status
- published
- Publisher
- Royal Soc Chemistry
- Journal
- Physical Chemistry Chemical Physics
- Organization
- Fakultät für Chemie ; Institut für Physikalische Chemie
- ISSN
- 1463-9084; 1463-9076
- Extent
- 7
- Language
- English
- Sponsor
- German Research Foundation [Su 121/5, SPP 1807]