Abstract
Type-V deep eutectic solvents (DESs) are a newly emerging unique class of solvents obtained by physical mixing and heating of non-ionic components. These solvents show deviation from the thermodynamic ideality. Compared to type-I to IV DESs, type-V DESs are less explored and their physical chemistry is in its nascent stage. In this work, we have chosen a type-V DES based on menthol-thymol (MT) for our working media. Solvent and rotational dynamics were studied with varying temperature using a well-known solvatochromic probe, Coumarin 153 (C153). We prepared the MT-based DES using a reported procedure at three molar ratios: 1 : 1 (M1T1), 1 : 1.5 (M1T1.5), and 2 : 1 (M2T1) of menthol (M) and thymol (T). Time-resolved emission spectra (TRES) were constructed with varying temperature. Utilizing TRES, the decay of the solvent correlation function (C(t)) was plotted. We have correlated the solvent relaxation time in these DESs as a function of viscosity. The time-resolved anisotropy decays were also collected to perceive the rotational relaxation dynamics of C153 as a function of temperature. The decay of solvent relaxation was found to be bi-exponential, and the average solvation time (〈τs〉) in M2T1 was found to be longer than those of M1T1.5 and M1T1. The rotational reorientation times (〈τrot〉) also follow the same trend. We have analysed the rotational dynamics of C153 in type-V DESs employing the Stokes-Einstein-Debye (SED) hydrodynamic model. The rotational dynamics in DESs demonstrate a good correlation with the SED model with a little deviation. In MT-based DESs, the solute's rotational relaxation times approach hydrodynamic stick boundary condition at low viscosity (or at high temperatures) for all molar compositions. Using the Arrhenius-type equations, we have correlated the activation energies for the rotational motion of C153, along with the viscous flow and non-radiative pathways for all the DESs.
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