Anion-Templated Supramolecular C3 Assembly for Efficient Inclusion of Charge-Dispersed Anions into Hydrogen-Bonded Networks

The binding properties and conformational adaptability of a known nitrate/sulfate receptor N,N′‐3‐azapentane‐1,5‐bis[3‐(1‐aminoethylidene)‐6‐methyl‐3H‐pyran‐2,4‐dione] (L) toward various charge‐dispersed monoanions (HSO3−, ClO4−, IO4−, PF6−, and SbF6−) are considered. These anions template the folding of three HL+ species through a self‐assembly process into a new hollow supramolecular trication. During the self‐assembly, all strong hydrogen‐bond donors of the podand become coordinatively saturated by interactions with the oxo functionalities from other HL+ molecules. In that way, only the weak hydrogen‐bond‐donating groups in the exterior part of the receptor are accessible for anion binding. The investigated anions are accommodated in the hydrophobic pockets of the isomorphous hydrogen‐bonded frameworks, which serve as a basis for selective crystallization from the highly competitive anion/solvent systems. This behavior is discussed in terms of size and geometry of the anions as well as the receptor’s coordination capabilities to provide the most favorable surroundings for guest inclusion both in solution and in the solid state. Who's in charge? Podand L, a selective NO3−/SO42− receptor, recognizes differences in charge density of the investigated oxo‐ and fluoroanions. Charge‐dispersed anions govern folding of HL+ to a hollow supramolecular macrocycle, with the anions anchored in the hydrophobic pockets of the hydrogen‐bonded structure (see figure). This behavior is discussed in terms of the size and geometry of anions as well as the receptor's coordination capabilities to provide the most favorable surroundings for guest inclusion.