Weak Interactions in Dimethyl Sulfoxide (DMSO)-Tertiary Amide Solutions: The Versatility of DMSO as a Solvent

The structures of equimolar mixtures of the commonly used polar aprotic solvents dimethylformamide (DMF) and dimethylacetamide (DMAc) in dimethyl sulfoxide (DMSO) have been investigated via neutron diffraction augmented by extensive hydrogen/deuterium isotopic substitution. Detailed 3 -dimensional structural models of these solutions have been derived from the neutron data via Empirical Potential Structure Refinement (EPSR). The intermolecular center-of-mass (CoM) distributions show that the first coordination shell of the amides comprises similar to 13-14 neighbors, of which approximately half are DMSO. In spite of this near ideal coordination shell mixing, the changes to the amide-amide structure are found to be relatively subtle when compared to the pure liquids. Analysis of specific intermolecular atom-atom correlations allows quantitative interpretation of the competition between weak interactions in the solution. We find a hierarchy of formic and methyl C-HmiddotmiddotmiddotO hydrogen bonds forms the dominant local motifs, with peak positions in the range of 2.5-3.0 A. We also observe a rich variety of steric and dispersion interactions, including those involving the O=C-N amide pi-backbones. This detailed insight into the structural landscape of these important liquids demonstrates the versatility of DMSO as a solvent and the remarkable sensitivity of neutron diffraction, which is critical for understanding weak intermolecular interactions at the nanoscale and thereby tailoring solvent properties to specific applications.

Automated summary

The structures of equimolar mixtures of DMF and DMAc in DMSO were studied using neutron diffraction and isotopic substitution. Detailed 3D structural models were derived from the neutron data. The first coordination shell of the amides consists of approximately 13-14 neighbors, half of which are DMSO. The changes to the amide-amide structure in the mixture are relatively subtle compared to the pure liquids. Analysis of atom-atom correlations reveals a hierarchy of hydrogen bonds and a variety of steric and dispersion interactions, providing insight into the weak intermolecular interactions in these liquids.