In Competition for Water: Hydrated Choline Chloride:Urea vs Choline Acetate:Urea Deep Eutectic Solvents

Unlike the archetypal deep eutectic solvent (DES) choline chloride:urea (ChCl:U), fundamental knowledge of the intermolecular network in choline acetate (ChOAc) DESs and how they change upon dilution is still missing. Here we jointly use UV resonance Raman (UVRR) and NMR spectroscopy to comparatively explore how the strength and distribution of hydrogen bonding and the solvation of the components are modified in ChOAc:U and ChCl:U with increasing hydration. Overall, Raman and NMR data indicate that ChOAc:U is continuously affected by hydration and, even at low water concentrations, undergoes a breakage of DES-DES interactions, with rapid solvation of the urea portion and full exchange of mobile protons. On the contrary, ChCl:U seems to maintain its structure as small interplays gradually occur between urea in the DES and the surrounding water molecules. The combined approach provides a multifaceted consistent description of the systems, outlining the crucial role of the anion in driving the structure and dynamics of the materials and then yielding valuable data toward the exploitation of DESs as tunable systems.