A disparity in solvatochromism of C[dbnd]O and S[dbnd]O vibrational probe: A study of structurally similar acetone and dimethyl sulfoxide

Abstract

Solvatochromic studies of small IR probes are beneficialto study the structural dynamics of biomolecules as well as measuring the strength of surrounding electric fields in condensed phases.Herein, we have investigated the CO and SO vibrational probes of structurally similar acetone and dimethyl sulfoxide respectively to compare the solvatochromism. Interestingly in water CO formed both one hydrogen bond and two hydrogen bond complexes wherein SO formed only two hydrogen bond complexes.Not only this, but we have also investigated how different solvents alter the IR spectra of the CO and SO vibrating modes during the interaction with α CH of acetone and DMSO respectively.The IR absorption spectra of CO of acetone altered after αdeuteration(acetoned6) in aprotic organic solvents as well as aqueous solvents. But, surprisingly for DMSO and DMSOd6, the IR spectra of SO mode remain intact during α isotopic exchange (CH3to CD3) in organic aprotic solvents but in strong coordinating polar protic solvents (D2O) it is altered remarkably. The equivalent frequency gap of CO of acetone and acetoned6 in organic solvents and water represent the no interaction of α CH/D with solvent molecules. Parallelly unaltered IR spectral signature of SO of both DMSO and DMSOd6 in aprotic organic solvent represents the stationary state of the ‘S’ atom and altered SO IR absorption in water signifies the different α CH and α C-D interaction with the surrounding water molecules. These results are the cautionary of perturbation on IR probe during α CH interaction with solvents as well as guest molecules.