Understanding of the interactions between azole-anion-based ionic liquids and 2-methyl-3-butyn-2-ol from the experimental perspective: the cage effect

Abstract

The interactions between azole-anion-based ionic liquids (AILs) and 2-methyl-3-butyn-2-ol (MBY) play an important role in AIL-promoted carboxylative cyclization of MBY with CO₂. To better understand the interactions between AILs ([P₆₆₆₁₄][Im], [P₆₆₆₁₄][4-MeIm], and [P₆₆₆₁₄][4-BrIm]) and MBY, a detailed investigation from the experimental perspective has been carried out in this study. The results show that the derivative of viscosity (η) with the mole fraction of AIL (x_AIL) of AIL + MBY mixtures appears to have the maximum value when x_AIL ≈ 0.3, while ¹H NMR chemical shifts of P-CH₂ of [P₆₆₆₁₄]⁺ reach the minimum value at x_AIL ≈ 0.3, indicating that [P₆₆₆₁₄]⁺ of AILs tend to self-aggregate. The interaction parameters (g_ji–g_ii) of the systems obtained from η by the Eyring-UNIQUAC equation are positive, and the difference between the bulk and local composition (x_i–x_ii) is always negative, indicating that AILs can interact with MBY. Moreover, excess molar volumes and isentropic compressibility deviations are all negative deviations and become more negative as the temperature increases, reaching a minimum value at x_AIL ≈ 0.30, indicating that azole-based anions can form H-bonds with MBY, and MBY molecules tend to enter the aggregates formed by AILs. Consequently, the cage effect is proposed to describe the interactions between AILs and MBY: MBY first enters the cage formed by the aggregation of [P₆₆₆₁₄]⁺, and then forms H-bonds with azole-based anions. Finally, the sizes of the particles of the [P₆₆₆₁₄][Im] + MBY mixture from dynamic light scattering increase first and then decrease with x_AIL, with the maximum of 122 nm at x_AIL ≈ 0.25, which confirms the rationality of the cage effect.