Abstract
In this study, two complementary approaches, affinity capillary electrophoresis (ACE) and quantum mechanical density functional theory (DFT) calculations, have been employed for quantitative characterization and structure elucidation of the complex between hexaarylbenzene (HAB)‐based receptor R and lithium ion Li^+^. First, by means of ACE, the apparent binding constant of LiR^+^ complex (K) in methanol was determined from the dependence of the effective electrophoretic mobilities of LiR^+^ complex on the concentration of lithium ions in the 25 mM Tris/50 mM chloroacetate background electrolyte (BGE) using non‐linear regression analysis. Prior to regression analysis, the effective electrophoretic mobilities of the LiR^+^ complex were corrected to reference temperature 25°C and constant ionic strength 25 mM. The apparent binding constant of the LiR^+^ complex in the above methanolic BGE was evaluated as log__K__ = 1.15±0.09. Second, the most probable structures of nonhydrated LiR^+^ and hydrated LiR^+^·3H~2~O complexes were derived by DFT calculations. The optimized structure of the hydrated LiR^+^·3H~2~O complex was found to be more realistic than the nonhydrated LiR^+^ complex because of the considerably higher binding energy of LiR^+^·3H~2~O complex (500.4 kJ/mol) as compared with LiR^+^ complex (427.5 kJ/mol).