Fluoride: solution- and solid-state structural binding probe.

Solid-state and solution studies were performed to determine if F(-) is encapsulated by anion hosts in both media. X-ray crystal structure determinations were compared with both (1)H and (19)F solution NMR data. Three hosts were studied: (1) two polyamide hosts, one with isophthaloyl spacers and the other with pyridine spacers, and (2) a polythioamide host with pyridine spacers. Binding studies showed that the pyridine-containing amide cryptand shows the highest affinity (K(a) > 10(5) in DMSO-d(6)), with the other hosts at least a factor of 10 lower. All of the cryptands appear to encapsulate F(-) in solution, where a deuterium-exchange reaction with DMSO-d(6) can be monitored by (19)F NMR. Four crystal structures are reported and compared: two for the pyridine-containing free base hosts and two for encapsulated F(-) complexes of the two amide-based cryptands.