The influence of the cation structure on the basicity-related polarity of ionic liquids

Abstract

The solvatochromic ThTCF probe responds to anion coordination. Correlations of UV/Vis data from ThTCF with various basicity-related polarity scales (Kamlet-Taft β, Freire EHB, Laurence β1) allow an evaluation of their physical significance.

Synthesis and photoinitiated polymerization of new ionic liquid methacrylates

“…An opposite behavior is expected for the α-value of the Kamlet-Taftparameters describing the hydrogen bond donating capability. Although similar π*-values of the Kamlet-Taftparameters were observed for TFl and TFAc indicating similarity in bipolarity/polarizability, the π*-value slightly increases in the order 29 : FAP < NTf 2 < TFl ¼ TFAc: Though both the β-value and π*-value of the Kamlet-Taft-parameters published in the literature 28,29 show a similar tendency for FAP < NTf 2 < TFl, the polarity parameters are also not in direct correlation with the polymerization rate as discussed above for the viscosity. This shows the high complex behavior of ionic liquids in the photoinitiated polymerization kinetics of ionic liquid monomers.…”

“…Though both the β ‐value and π *‐value of the Kamlet–Taft‐parameters published in the literature 28,29 show a similar tendency for FAP < NTf 2 < TFl, the polarity parameters are also not in direct correlation with the polymerization rate as discussed above for the viscosity. This shows the high complex behavior of ionic liquids in the photoinitiated polymerization kinetics of ionic liquid monomers.…”

“…However, polarity discussion of ionic liquids is more complex compared to viscosity discussion because various methods have been used for polarity investigation of ionic liquids on the one hand and the results strongly depend on the interactions between the single probes used and the ionic liquids on the other hand 28,29 . As shown in the reference, 28 the β ‐value of the Kamlet–Taft‐parameters increases in the order: …”

Empirical Hydrogen Bonding Donor (HBD) Parameters of Organic Solvents Using Solvatochromic Probes – A Critical Evaluation

“…Recently, we analysed basicity-related empirical polarity scales of room temperature ionic liquids (RTIL) with respect to N of the RTIL to check whether dipolar influences have an influence on the measurand. [87] In this context, the Laurence β 1 parameter of RTILs was found to be very suitable as basicity scale, as it does not give a correlation with N. [87] Currently, Laurence β 1 parameters for organic solvents, including various HBD solvents, are determined experimentally by the solvatomagnetic method using 19 F NMR spectroscopy of fluorine-containing probe molecules. [11c] Therefore, we examined the correlation of β 1 as a function of D HBD to test whether the lack of correlation with volume properties also applies to the β 1 parameter for organic solvents.…”

The Global Polarity of Alcoholic Solvents and Water – Importance of the Collectively Acting Factors Density, Refractive Index and Hydrogen Bonding Forces

“…Section A of the Supporting Information summarises some aspects on "global polarity" from the literature showing the problem when different concepts [(Lorentz-Lorenz, Debye equation, linear solvation energy relations (LSER)] are considered alternatively. [10][11][12][13][14][15][16][17][18][19][20] According to the Lorentz-Lorenz or Debye equation, the influence of the "global polarity" of the solvent volume will be analyzed in terms of their molar concentration N. [11,13,14,20] N is an important physical quantity that represents the relationship between density 1 and molar mass M, regardless of its state of aggregation [Eq. (2)].…”