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

UV/Vis absorption data of (E)-4-(2-[5-{4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl}thiene-2-yl]vinyl)-2-(dicyano-methylene)-3-cyano-5,5-dimethyl-2,5-dihydrofuran (ThTCF) as a solvatochromic probe is applied to examine the anion coordination strength (e.g. of N(CN)(2), BF4, PF6, N(Tf)(2), CF3COO) as a function of the cation structure of ionic Liquids. Several 1-n-alky-3-methylimidazolium- and tetraalkylammonium CH3-NR3+-based ILs with different n-alkyl chain lengths (R = -C4H9, -C6H11, -C8H17, -C10H21) are considered. UV/Vis absorption data of ThTCF show subtle correlations with hydrogen bond accepting (HBA) ability-related measurands such as Kamlet-Taft beta, Freire's E-HB, and Laurence beta(1) parameter as a function of anion and cation structure. The different influence of the n-alkyl chain length of imidazolium- and tetraalkylammonium-based ILs on the dipolarity and HBA strength is confirmed by comparison with the N-14 isotropic hyperfine coupling constants (A(iso)) of a positively (CATI) and negatively charged spin probe (TSKCr) of TEMPO-type [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl] and quantum chemically derived dipoles of the cations. The A(iso) values correlate with the absorption energy of ThTCF and E-HB, but in different ways depending on the anion or charge of the spin probe. In a final discussion of the beta, E-HB, and beta(1) scales in relation to ThTCF, the importance of the molar concentration N of ionic Liquids for the physical significance of the respective parameters is discussed.