Novel crownophanes with three pyridine moieties (pyridinocrownophanes 4 and 5) were prepared by means of intramolecular [2+ 2] photocycloaddition of vinylpyridine derivatives. In the liquid–liquid extraction of heavy metal cations, 4 and 5 exhibited high efficiency toward Ag+. Comparing the high extractability and complexing stability constant for Ag+ to those of the corresponding pyridinocrownophanes 2 and 3 and observing the 1H NMR ...