New ICT probes: synthesis and photophysical studies of N-phenylaza-15-crown-5 aryl/heteroaryl oxadiazoles under acidic condition and in the presence of selected metal ions

Abstract

Molecular probes 6 and 7, incorporating N-phenylaza-15-crown-5 and aryl/heteroaryl oxadiazole have been designed to function as the new intramolecular charge transfer (ICT) probes. Photophysical properties have been studied under acidic condition as well as in the presence of selected metal ions, Ca 2+, Ba 2+, Mg 2+, Na +, K +, and Li +. The changes in the ICT character of the probes, following the addition of trifluoroacetic acid, were interpreted in terms of site and degree of protonations. Based on the cation affinity, the ICT bands in both UV–vis and emission spectra experienced varying degrees of blue shifts due to removal of the aza-crown ether nitrogen from conjugation. The cation-induced spectral shifts and the stability constants revealed binding strength in the order Ca 2+>Ba 2+≫Li +>Na +>K +>Mg 2+. Competitive experiments performed in a matrix of ions also indicated superior interaction of 6 and 7 with Ca 2+. The excited state decay profiles remained largely unperturbed in the presence of metal ions. The studied probes displayed positive solvatochromism and the Stokes shifts and excited state lifetimes increased with increasing solvent polarity. These findings can be rationalized by invoking highly polar nature of the emittive states. The chemoionophores 6 and 7 constitute potentially interesting Ca 2+ sensitive probes due to their relatively high binding interaction for Ca 2+ (log K s=3.55–3.10) vis-a-vis that of biologically interfering Mg 2+ (log K s=1.67–1.30).