Solvation structure and dynamics of coumarin 153 in an imidazolium-based ionic liquid with chloroform, benzene, and propylene carbonate

Abstract

In order to determine the self-diffusion coefficients D of all the species in the solutions at 298.2 K, ¹H and ¹⁹F NMR diffusion ordered spectroscopy (DOSY) has been conducted on coumarin 153 (C153) in binary mixed solvents of an imidazolium-based ionic liquid (IL), 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (C₁₂mimTFSA), with three molecular liquids (MLs) of chloroform (CL), benzene (BZ), and propylene carbonate (PC) as a function of ML mole fraction x_ML. Below x_ML ≈ 0.8, the D values of each species do not significantly depend on the MLs. However, above this mole fraction, the diffusion of C153 becomes smoother in the order of BZ ≈ CL > PC systems. The interactions among C153, C₁₂mim⁺, TFSA⁻, and ML molecules have been investigated using infrared (IR) and ¹H and ¹³C NMR spectroscopic techniques. The relations of the diffusion of the species with the interactions among them have been discussed on the molecular scale. In the IL solution, the C153 carbonyl oxygen atom is hydrogen-bonded with the imidazolium ring C²–H atom of C₁₂mim⁺. C₁₂mim⁺ also forms an ion pair with TFSA⁻. Thus, C153, C₁₂mim⁺, and TFSA⁻ cooperatively move in the CL and BZ solutions at a lower ML content, x_ML < ∼0.8. On the other hand, at a higher ML content, x_ML > ∼0.8, the C153 molecule diffuses with CL and BZ molecules because of the hydrogen bonding between the C153 carbonyl O atom and the CL H atom and the π–π interaction between the C153 and BZ ring planes, respectively. For the PC system, the change in the relative self-diffusion coefficients of each species with increasing x_ML differs from those for the CL and BZ systems because of both hydrogen bonding donor H and acceptor O atoms of PC for C153, the IL cation and anion, and PC themselves.