Azo-hydrazone tautomerism in a simple coumarin azo dye and its contribution to the naked-eye detection of Cu2+ and other potential applications

Abstract

A new tailor-made azo dye of coumarin connected to phenolic derivative is presented herein. Azo-hydrazone tautomerism in aqueous solution of the dye was observed and studied using spectroscopic assays such as ¹H NMR, absorption and emission assays, and theoretical studies. Tautomerism was attributed to the presence of a labile phenolic hydrogen in the ortho position to the azo functionality and the hydrazone was found to be the more dominant tautomer. Influence of metal ions on the azo-hydrazone chemical equilibrium and how the accompanying colour and spectroscopic changes can be exploited for various functions, especially the detection and quantification of Cu²⁺ in aqueous environments was explored. The presence of Cu²⁺ affects the azo-hydrazone equilibrium resulting in visual appearance and spectroscopic changes and the likely binding sites for Cu²⁺ were evaluated. Cu²⁺ pushes the azo-hydrazone equilibrium towards the more conjugated form and the presence of other metal ions does not have any perceivable impact on this mechanism. The dye showed potential applications as a sensor in colorimetric and spectroscopic detection and quantification of Cu²⁺ in domestic and environmental water samples, photo-imprinting and as a logic gate. The limits of detection (LOD) and quantification (LOQ) for Cu²⁺ were found to be 0.0779 mg/L and 0.236 mg/L, respectively, much lower than the World Health Organization (WHO) guideline limit for Cu²⁺ levels in drinking water.

Keywords: Azo coumarin; Azo-hydrazone tautomerism; Colorimetry and photo-imprinting; Copper detection and quantification.