Shape-Selective Recognition of Quaternary Ammonium Chloride Ion Pairs

Synthetic receptors that recognize ion pairs are potentially useful for many technical applications, but to date there has been little work on selective recognition of quaternary ammonium (Q⁺) ion pairs. This study measured the affinity of a tetralactam macrocycle for 11 different Q⁺·Cl^- salts in chloroform solution. In each case, NMR spectroscopy was used to determine the association constant ( K_a) and the structure of the associated complex. K_a was found to depend strongly on the molecular shape of Q⁺ and was enhanced when Q⁺ could penetrate the macrocycle cavity and engage in attractive noncovalent interactions with the macrocycle's NH residues and aromatic sidewalls. The highest measured K_a of 7.9 × 10³ M^-1 was obtained when Q⁺ was a p-CN-substituted benzylic trimethylammonium. This high-affinity Q⁺·Cl^- ion pair was used as a template to enhance the synthetic yield of macrocyclization reactions that produce the tetralactam receptor or structurally related derivatives. In addition, a permanently interlocked rotaxane was prepared by capping the end of a noncovalent complex composed of the tetralactam macrocycle threaded by a reactive benzylic cation. The synthetic method provides access to a new family of rotaxanated ion pairs that can likely act as anion sensors, molecular shuttles, or transport molecules.