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

• Published in: Inorganica Chimica Acta 2019-03, Vol.487, p.120-127
• Main Authors: Ghildiyal, Namrata, Pant, Geeta Joshi nee, Rawat, M.S.M.
• Format: Article
• Language: English
• Subjects: Acetonitrile; Alkali metals; Antibiotics; Benzo crown; Cation recognition; Cations; Cell membranes; Chemical synthesis; Chloroform; Complexes; Crown ethers; Dipole interactions; Ethers; Fluorescence; Fluorescent indicators; Fluorides; Halides; Macromolecules; NMR; Nuclear magnetic resonance; Potassium; Potassium fluoride; Recording
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2018.11.052

A pictorial representation of two benzo crown ethers assembling together to accommodate a potassium ion to form 2:1 ligand-metal ion complex. The cation is held in the cavity by ion-dipole interactions. The coordination number of the potassium ion is ten. Complexation enhanced fluorescence produced by suppression of PET mechanism is masked by FRET. [Display omitted] •Complexes of two crown ethers, benzo-15-crown-5 and dibenzo-15-crown-5, were prepared with potassium halides in acetonitrile and characterized by FTIR, UV, ESI-MS, 1H NMR and 13C NMR techniques.•Fluorescence studies showed that the fluorescence emission intensity is a residual value after suppression of photoinduced electron transfer (PET) mechanism and energy resonance transfer (FRET) mechanism operative in complexes of benzo-15-crown-5 and dibenzo-15-crown-5.•These complexes can be used as FRET based sensors for potassium ions. 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.