On the molecular basis of H2O/DMSO eutectic mixtures by using phenol compounds as molecular sensors: a combined NMR and DFT study

Abstract

NMR and DFT studies of phenol compounds as molecular sensors were carried out to investigate H₂O/DMSO eutectic mixtures at a molecular level. The experimental ¹H NMR chemical shifts of the OH groups, δ_exp(OH), of phenol, paracoumaric acid, and vanillic acid show maximum deshielding and, thus, hydrogen bond interactions in the range of mole fractions 0.20 < χ(DMSO) < 0.33. In the mole fractions χ(DMSO) < 0.2, a progressive decrease in δ_exp(OH) was observed which demonstrates a decrease in hydrogen bond interactions at infinite dilution in H₂O, despite the increase in the number of available hydrogen bond acceptor and donor sites. DFT calculated δ_calc(OH) of minimum energy solvation clusters were shown to be in reasonable agreement with the pattern in experimental δ_exp(OH) data. The chemical shift deshielding and, thus, increased hydrogen bond interactions in the natural product + DMSO + nH₂O (n = 2, 3) solvation clusters, relative to complexes in DMSO or H₂O solutions, cannot be attributed to a single structural parameter of the cooperative interactions between H₂O and DMSO molecules with the phenol OH groups of the natural products. The minimum energy conformers of phenol compounds + 2H₂O + DMSO complexes are in excellent agreement with a recent low temperature neutron diffraction experiment of 3D₂O + DMSO and demonstrate a general structural motif of solvation complexes. The combined use of ¹H NMR and DFT studies with emphasis on δ(OH) of phenol compounds, as molecular sensors, can provide an effective method for the study of solute–solvent interactions at the atomic level.