A well-defined “four-wall” capsule (3) was constructed based on the coordination-driven self-assembly of a tetratopic pyridine-functionalized calix[4]pyrrole cavitand with four stabilizing pyridine···Ag+···pyridine coordination bonds in N,N-dimethylformamide (DMF). Capsule was 3 characterized by means of various techniques, including 1H nuclear magnetic resonance (NMR) spectroscopy, diffusion ordered NMR spectroscopy (DOSY), electrospray ionization mass spectrometry (ESI-MS), and single crystal X-ray diffraction analyses. The tetra-α-meso-pyridyl extended calix[4]pyrrole ligand 2 and the corresponding dimeric capsule 3 were found to recognize selectively the fluoride anion over other halide anions (chloride, bromide, and iodide anions) in DMF. Cavitand 2 was found to bind and release Ag+ via a fast equilibrium exchange process on the NMR timescale, whereas the fluoride binding of both 2 and capsule 3 proved slow on the NMR timescale. The transformation among multiple molecular states, viz. monomeric form 2, capsule 3, and their corresponding fluoride-bound complexes F−⊂2 and 2F−⊂3, could be modulated by the addition of silver, fluoride, and chloride ions.

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