Synthesis, characterization and electrochemical properties of two new calix[4]arene derivatives bearing two ferrocene imine or ferrocene amine units at the upper rim

Abstract

A novel calix[4]arene derivative with two ferrocenyl Schiff-base groups at the upper rim 3 has been synthesized from 5,17-diformyl-25,27-dipropoxy-26,28-dihydroxy calix[4]arene and 4-ferrocenylaniline via condensation reaction. Reduction of 3 with sodium borohydride led to calix[4]arene derivative 4 with two amino ferrocenyl groups at the upper rim. The ferrocenyl Schiff-base calix[4]arene and its corresponding reduced amine have been purified and characterized by elemental analysis, 1H NMR, FTIR, Mass and UV–vis spectral data. Electrochemical properties of compounds 3 and 4 have been investigated. Cyclic voltammograms of 3 and 4 show reversible redox couples of ferrocene/ferrocinium at E 1/2=0.401 V and 0.346 V, respectively. Electrochemical studies show these redox active compounds electrochemically recognize trivalent lanthanides La 3+ and Ce 3+ and divalent Pb 2+ and Cu 2+cations. With ferrocenyl Schiff-base calix[4]arene 3 an anodic shift as large as 130 mV is observed on addition of one equivalent of Ce 3+ ion. Also extraction properties of compound 4 towards some metal cations have been described. It has been observed that compound 4 has a good selectivity for metal cations Fe 3+, Cu 2+, Pb 2+ and Cd 2+ against Ni 2+ and Co 2+.