Does Viscosity Decoupling Guarantee Dynamic Heterogeneity? A Clue through an Excitation and Emission Wavelength-Dependent Time-Resolved Fluorescence Anisotropy Study. 2023

Ejaj Tarif, and Nilimesh Das, and Pratik Sen
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208 016, Uttar Pradesh, India.

Traditionally, deviation from Stokes-Einstein-Debye (SED) relation in terms of viscosity dependence of medium dynamics, i.e., with p ≠ 1, is taken as a signature of dynamic heterogeneity. However, it does not guarantee medium heterogeneity, as the decoupling may also originate from the deviation of the basic assumption of SED. Here, we developed a method to find a stronger relation between viscosity decoupling (p ≠ 1) and dynamic heterogeneity in terms of rotational motion. Our approach exploited the fact that in heterogeneous media, a solvatochromic probe will be solvated to a different extent at different microdomains (subpopulations), and photoselection of these subpopulations can be achieved by excitation or emission wavelength-dependent measurements. We hypothesized that the dynamics of a homogeneous system might show viscosity decoupling, but the extent of decoupling at different excitations (or at different emissions) should not be different. On the other hand, in a heterogeneous medium, this extent of viscosity decoupling (p-value) should be different at different excitations (or at different emissions). As proof of concept, we investigated three versatile solvent media: squalane (viscous molecular liquid), 1-ethyle-3-methylimidazolium ethyl sulfate ionic liquid (IL), and [0.78 acetamide + 0.22 LiNO3] deep eutectic solvent (DES). We found that squalane is homogeneous, although it shows fractional viscosity dependence (p ≠ 1). Interestingly, mild heterogeneity in IL and significant heterogeneity in the DES were observed. Overall, we conclude that the difference in the p-value as a function of excitation (or emission) wavelength-dependent might be a superior way for the detection of dynamic heterogeneity.

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