Log K, {Delta}H, and {Delta}S values for interactions of a series of pyridinoazacrown ethers each bearing a phenol arm (2-6) and two macrocycles each bearing a pyridine arm (7, 8) with Na{sup +}, K{sup +}, Tl{sup +}, and Ag{sup +} have been determined in absolute methanol at 25{degrees}C by calorimetric titration. In each case, the complex stability has the sequence Na{sup +} < K {sup +} < Tl{sup +} {much_lt} Ag{sup +}. The phenol-armed macrocycles exhibit selectivity of more than 4 orders of magnitude for Ag{sup +} over Na{sup +}, K{sup +}, and Tl{sup +}. Attachment of a pendant phenol arm having various substituents to parent macrocycle 1 increases the binding abilities of the resulting ligands. Substituents on the para position of the phenol arm have an appreciable effect on cation-binding constants. Good Hammett correlations are found by plotting log K values vs {sigma}{sub p} for interactions of five phenol-armed macrocyclic ligands (2-6) with Na{sup +}, K{sup +}, and Tl{sup +}. The complexation has been characterized by means of {sup 1}H NMR and UV-visible spectroscopic, and X-ray crystallographic methods. The study indicates that the phenol OH group of 2-6 is capable of forming an intramolecular hydrogen bond with the macroringmore » nitrogen atom and that the complexation in absolute methanol generally does not deprotonate these phenols. In the crystal structure of the Na{sup +} -3 complex, the Na{sup +} is coordinated to all seven of the donor atoms of the ligand and two Na{sup +} -3 complexes join together to form a dimer. The dimer contains an intermolecular hydrogen bond formed between the phenol hydrogen atom of one ligand and the phenolate group of a centrosymmetrically related ligand and two {pi}-{pi} stacking interactions between the electron-deficient pyridine ring of one molecule and the electron-rich phenol ring of the other. 36 refs., 5 figs., 6 tabs.« less