Azocalixarenes: Synthesis, Characterization, Complexation, Extraction, Absorption Properties and Thermal Behaviours

Azocalixarenes, which have a conjugated chromophore azo (–N=N–) group in p-positions, are synthesized in “one-pot” procedures in satisfactory yields. Their structures in the solid and solution are elucidated by UV–vis, FT-IR, ¹H and ¹³C NMR spectroscopic methods as well as elemental analysis techniques. Some of them are complexed with metal ions (alkali, alkaline-earth and transition metal ions) under neutral conditions. A wide variety of applications is expected by the functionalization of the side arms. The selective liquid–liquid extraction of various alkali, alkaline-earth and transition metal cations from the aqueous phase to the organic phase is carried out by using azocalixarenes. Furthermore, the synthesized azocalixarenes are utilized for selective extraction of Fe³⁺ cations from the aqueous phase to the organic phase. The effects of varying pH and solvent upon the absorption ability of azocalixarenes substituted with electron-donating and electron-withdrawing groups at their o-, m-, p-positions are examined. The thermal behaviours of azocalixarenes containing upper rim functionalized groups are investigated by means of thermogravimetry (TG), differential thermal analysis (DTA) and differential thermogravimetry (DTG).