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Issue 39, 2016
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Subtle solvation behaviour of a biofuel additive: the methanol complex with 2,5-dimethylfuran

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Abstract

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.

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

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Publication details

The article was received on 04 Aug 2016, accepted on 14 Sep 2016 and first published on 21 Sep 2016


Article type: Paper
DOI: 10.1039/C6CP05413G
Citation: Phys. Chem. Chem. Phys., 2016,18, 27265-27271
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    Subtle solvation behaviour of a biofuel additive: the methanol complex with 2,5-dimethylfuran

    A. Poblotzki, J. Altnöder and M. A. Suhm, Phys. Chem. Chem. Phys., 2016, 18, 27265
    DOI: 10.1039/C6CP05413G

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