Picking on Carbonate: Kinetic Selectivity in the Encapsulation of Anions.

Supramolecular hosts bind to inorganic anions at a fast rate and select them in proportion with thermodynamic stability of the corresponding [anion⊂host] complexes, forming in a reversible manner. In this study, we describe the action of hexapodal capsule 1 and its remarkable ability to select anions based on a large span of rates by which they enter this host. The thermodynamic affinity of 1 toward eighteen anions extends over eight orders of magnitude (0<Ka <108  M-1 ; 1 H NMR spectroscopy). The capsule would retain CO3 2- (Ka =107  M-1 ) for hours in the presence of eleven competing anions, including stronger binding SO4 2- , HAsO4 2- and HPO4 2- (Ka =107 -108  M-1 ). The observed selection resulted from 1 possessing narrow apertures (ca. 3×6 Å) comparable in size to anions (d=3.5-7.1 Å) slowing down the encapsulation to last from seconds to days. The unorthodox mode of action of 1 sets the stage for creating hosts that pick anions by their ability to access the host.