Stabilities in Water of Alkali Metal Ion Complexes with Dibenzo-24-crown-8 and Dibenzo-18-crown-6 and Their Transfer Activity Coefficients from Water to Nonaqueous Solvents

Stability constants KML for the 1:1 complexes of Na+, K+, Rb+, and Cs+ with dibenzo-24-crown-8 (DB24C8) and dibenzo-18-crown-6 (DB18C6) in water have been determined by a capillary electrophoretic technique at 25°C. The KML sequence is Na+ < K+ < Rb+ < Cs+ for DB24C8 and Na+ < K+ > Rb+ > Cs+ for DB18C6. Compared with DB18C6, DB24C8 exhibits higher selectivity for K+ over Na+, but lower selectivity for K+, Rb+, and Cs+. To evaluate the solvation of the complexes in water, their transfer activity coefficients sγH2O between polar nonaqueous solvents and water have been calculated. The sγH2O values provide the following information: interactions with water of the metal ions and of the crown-ether oxygens are greatly reduced upon complexation and the complexes undergo hydrophobic hydration in water; the character of each alkali metal ion in solvation is more effectively masked by DB24C8 than by DB18C6, because of the larger and more flexible ring structure of DB24C8. Solvent effects on the complex stabilities are discussed on the basis of the sγH2O values.