Benzo-15-crown-5 (2,3,5,6,8,9,11,12-octahydrobenzo[b][1,4,7,10,13]pentaoxacyclopentadecine) and dibenzo-15-crown-5 (6,7,9,10,17,18-hexahydrodibenzo[b,h][1,4,7,10,13]pentaoxacyclopentadecine as fluorescent probes for physiologically important potassium ion

Abstract

Cation recognition plays a vital role in defining advanced functions of macromolecules in nature. An example of such an interaction is the action of a natural antibiotic, valinomycin, that behaves as a potassium ionophore. It encages the cation to transport it across a cell membrane and easily releases it inside the cell. Macrocyclic complexes of some crown ethers mimick alkali ion interactions with natural ionophores. We have synthesized complexes of two crown ethers namely benzo-15-crown-5 (2,3,5,6,8,9,11,12-octahydrobenzo[b][1,4,7,10,13]pentaoxacyclopentadecine) and dibenzo-15-crown-5 (6,7,9,10,17,18-hexahydrodibenzo[b,h][1,4,7,10,13]pentaoxacyclopentadecine with potassium halides (fluoride, chloride, bromide and iodide) in acetonitrile and characterized them by IR, UV, ESI-MS, 1H NMR and 13C NMR techniques. The effect of the anion on the stability of the complexes was observed by 1H NMR studies. The alkali metal ion is held to the oxygen donor atoms of the macrocyclic ring by ion-dipole interactions. The potential of the small ring oxacrown ethers, benzo-15-crown-5 and dibenzo-15-crown-5, to act as probes for potassium ions in dilute solutions (4.1 × 10−4 M) was investigated by recording the variation in the fluorescence spectra of benzo-15-crown-5 and dibenzo-15-crown-5 on complexation with potassium fluoride in acetonitrile and chloroform. The rigidity of the macrocyclic ring and proximity of fluorophore units affected the fluorescence intensity of the complexes.