Calix4pyrrole as a Chloride Anion Receptor: Solvent and Counter-Cation Effects

摘要

The interaction of calixpyrrole with several chloride salts has been studied in the solid state by X-ray crystallography as well as in solution by isothermal titration calorimetry (ITC) and ¹H NMR spectroscopic titrations. The titration results in dimethylsulfoxide, acetonitrile, nitromethane, 1,2-dichloroethane and dichloromethane, carried out using various chloride salts, specifically tetraethylammonium (TEA), tetrapropylammonium (TPA), tetrabutylammonium (TBA), tetraethylphosphonium (TEP), tetrabutylphosphonium (TBP), and tetraphenylphosphonium (TPhP) showed no dependence on method of measurement. The resulting affinity constants (Ka's), on the other hand, were found to be highly dependent on the choice of solvent with Ka's ranging from 10²−10⁵ being recorded in the test solvents used for this study. In dichloromethane a strong dependence on the counter-cation was also seen, with the Ka's for the interaction with chloride ranging from 10²−10⁴. In the case of TPA, TBA and TBP the ITC data could not be fit to a 1:1 binding profile.