A molecular capsule (<b>1</b>) consisting of two calix[4]pyrroles connected via ethylene diamide linkers has been prepared as an anion receptor. ¹H NMR spectroscopic studies carried out in CD₂Cl₂ revealed that receptor <b>1</b> recognizes a variety of anions with different binding modes and stoichiometries. For instance, receptor <b>1</b> binds fluoride and acetate with 1:2 receptor/anion stoichiometry and other test anions with 1:1 stoichiometry in solution when their respective tetrabutylammonium (TBA⁺) salts were used. In contrast, with tetraethylammnium (TEA⁺) salts, receptor <b>1</b> forms 1:2 complexes with chloride and bromide in addition to fluoride, overcoming expected Columbic repulsions between the anions co-bound in close proximity. Receptor <b>1</b> is also able to bind oxoanions, such as oxalate (C₂O₄^2-), dihydrogen phosphate (H₂PO₄^-), sulfate (SO₄^2-), and hydrogen pyrophosphate (HP₂O₇^3-), in the form of 1:1 complexes as the result of presumed cooperation between the two calix[4]pyrrole subunits. The selectivity of receptor <b>1</b> for fluoride versus dihydrogen phosphate varies depending on their relative concentrations. For instance, in the presence of less than 1.0 equiv of an equimolar mixture of fluoride and dihydrogen phosphate, receptor <b>1</b> shows high selectivity for dihydrogen phosphate. In contrast, in the presence of ≥2.0 anion equiv, receptor <b>1</b> binds fluoride preferentially, forming a 1:2 complex. Moreover, when treated with F^-, the preformed 1:1 H₂PO₄^- complex of receptor <b>1</b> is converted to the corresponding 1:2 receptor/fluoride complex with the release of the prebound dihydrogen phosphate anion. As inferred from gas-phase computations, this seemingly counterintuitive behavior is rationalized in terms of the precomplexed dihydrogen phosphate serving to reduce the reorganization energy required to bind two fluoride anions. The presence of a water molecule in addition to the bound fluoride anions may also favor the formation of the 1:2 F^- complex. The present study provides a new approach for fine-tuning the binding selectivity of polytopic anion receptors.

[This corrects the article DOI: 10.1039/D4SC03760J.].