Calix[4]azacrowns: self-assembly and effect of chain length and O-alkylation on their metal ion-binding properties

Both the consequences of 1,3-cyclization of calix[4]arenes by diamide formation, and the effect of 2- and 2,4-alkoxycarbonylmethylation of two 1,3-bridged calix[4]azacrowns on their metal ion-binding capacities have been studied by synthesis of the derivatives in their cone conformation and measurement of the stability constants for their complexation in a range of alkaline earth and transition metal cations. In these two cases, the conformation of the ligand in the solid state has been defined in detail by a crystal structure determination. In the first case, a tubular architecture performing methanol channels is displayed, however, in the second case a zigzag architecture generated by a chloroform network connecting calixarene molecules is present. Speciation in solution appears to be limited to the formation of 1:2 and/or 1:1 and/or 2:1 (M–L) complexes, depending on the system, with values of the stability constants determined by absorption spectroscopy in acetonitrile, lying in the ranges log β12 ca. 10, log β11 ca. 2–5, and log β21 ca. 7–9. There is evidence for selectivity toward Cu(II) and for some unexpected anion effects. None of these ligands appear to be an efficient extractant for the metals as their picrate.