Syntheses of novel calix[4]arene hydrazone-based receptors and their cooperative complexation with soft and hard metal ions

Abstract

Four novel calix[4]arene hydrazone-based receptors 3a–d were prepared in yields of 69–87% by condensating formylated calix[4]arene ester (2) with salicylyl hydrazine, 2,4-dinitrophenyl hydrazine, nicotinyl hydrazine or phenyl thiosemicarhazide, respectively. New compounds were characterized through elemental analysis, IR, ESI–MS, 1H NMR studies. Compounds 3a–d containing two binding sites had the complexation abilities for hard and soft cations concurrently. The noncompetitive extracting experiments showed compounds 3a–d were excellent receptors for hard and soft metal cations. The competitive extracting experiments exhibited the cooperative complexation in binding hard and soft metal cations and compound 3a possessed outstanding selectivity for Na+ and Hg2+. The IR spectra of compound 3a before and after complexation revealed that the soft metal cation was binded in the cavity composed of hydrazone groups and azo groups at the upper rims of calix[4]arene units and hard metal cations was binded in cavity composed of ester groups and phenolic hydroxyl groups at the lower rims of calix[4]arene units.