Anion binding behavior of heterocycle-strapped calix[4]pyrroles

A comparative study of the halide and benzoate anion binding properties of a series of phenyl, pyrrole, and furan-strapped calix[4]pyrroles has been carried out. These receptors, which have previously been shown to bind the chloride anion (Yoon et al., Angew. Chem., Int. Ed. 47(27):5038-5042, 2008), were found to bind bromide and benzoate anion (studied as the corresponding tetrabutyl-ammonium salts) with near equal affinity in acetonitrile, albeit less well than chloride, as determined from ITC measurements or NMR spectroscopic titrations. This stands in marked contrast to the parent octamethylcalix[4]pyrrole, where the carboxylate anion affinities are substantially higher than those for bromide anion under identical conditions. This finding is rationalized in terms of tighter binding cavity present in the strapped systems. For all three anions for which quantitative data could be obtained (i.e., Cl(-), Br(-), PhCO(2) (-)), the pyrrole-strapped system displayed the highest affinity, although the relative enhancement was found to depend on the anion in question. In the specific case of fluoride anion binding to the pyrrole-strapped receptor, two modes of interaction are inferred, with the first consisting of binding to the calix[4]pyrrole via NH-anion hydrogen bonds, followed by a process that involves deprotonation of the strapped pyrrolic NH proton. A single crystal X-ray diffraction analysis provides support for the first of these modes and further reveals the presence of a methanol molecule bound to the fluoride anion.