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

2016 | journal article. A publication with affiliation to the University 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 Physics18(39) pp. 27265​-27271​.​ DOI: https://doi.org/10.1039/c6cp05413g 

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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]

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