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Issue 42, 2013
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Investigation of solute–solvent interactions in phenol compounds: accurate ab initio calculations of solvent effects on 1H NMR chemical shifts

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Abstract

Accurate 1H chemical shifts of the –OH groups of polyphenol compounds can be calculated, compared to experimental values, using a combination of DFT, polarizable continuum model (PCM) and discrete solute–solvent hydrogen bond interactions. The study focuses on three molecular solutes: phenol, 4-methylcatechol and the natural product genkwanin in DMSO, acetone, acetonitrile, and chloroform. Excellent linear correlation between experimental and computed chemical shifts (with the GIAO method at the DFT/B3LYP/6-311++G(2d,p) level) was obtained with minimization of the solvation complexes at the DFT/B3LYP/6-31+G(d) and DFT/B3LYP/6-311++G(d,p) level of theory with a correlation coefficient of 0.991. The use of the DFT/B3LYP/6-31+G(d) level of theory for minimization could provide an excellent means for the accurate prediction of the experimental OH chemical shift range of over 8 ppm due to: (i) strong intramolecular and solute–solvent intermolecular hydrogen bonds, (ii) flip-flop intramolecular hydrogen bonds, and (iii) conformational effects of substituents of genkwanin. The combined use of ab initio calculations and experimental 1H chemical shifts of phenol –OH groups provides a method of primary interest in order to obtain detailed structural, conformation and electronic description of solute–solvent interactions at a molecular level.

Graphical abstract: Investigation of solute–solvent interactions in phenol compounds: accurate ab initio calculations of solvent effects on 1H NMR chemical shifts

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Publication details

The article was received on 29 Jul 2013, accepted on 05 Sep 2013 and first published on 09 Sep 2013


Article type: Paper
DOI: 10.1039/C3OB41556B
Citation: Org. Biomol. Chem., 2013,11, 7400-7411
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    Investigation of solute–solvent interactions in phenol compounds: accurate ab initio calculations of solvent effects on 1H NMR chemical shifts

    M. G. Siskos, V. G. Kontogianni, C. G. Tsiafoulis, A. G. Tzakos and I. P. Gerothanassis, Org. Biomol. Chem., 2013, 11, 7400
    DOI: 10.1039/C3OB41556B

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