Anomalous Infrared Absorbance of S═O: A Perturbation Study of α-C–H/D

Solvatochromic shifts of S═O vibrational probes describe the strength of the surrounding electric fields and the hydrogen bonding status. Herein, we demonstrated how the solvents alter the infrared (IR) spectra of the S═O vibrating mode. The experimental measurement of the involvement of α-H/D isotopic interactions with different solvents and their effects on the IR absorbance spectra of the vibrational probe provides detailed knowledge of the microsolvation environment despite the complexity of overlapping bands in the spectra. Herein, we discover how the solvents interact differently with DMSO and DMSO-d6, while being electronically and structurally the same. Interestingly, the IR spectrum of the S═O mode remains unaltered during α-isotopic replacement in the presence of aprotic solvents (acetone, acetonitrile, and dichloromethane), but in strongly coordinating polar solvents (D2O), it is altered remarkably. There is a lack of quantitative information about the influence of the α-H atom or α-isotopic substitution on the vibrational probe in the literature. Our experiments provide a detailed molecular understanding of the structure of DMSO in DMSO–solvent binary mixtures. As DMSO plays an important role in virtually all subdisciplines of chemistry and biology, we believe that our work will be of interest to a large diversity of studies in these fields.