Physicochemical and Ion-Sensing Properties of Benzofurazan-Appended Calix[4]arene in Solution and on Gold Nanoparticles: Spectroscopy, Microscopy, and DFT Computations in Support of the Species of Recognition

A calix[4]arene conjugate (L) functionalized at the lower rim with a benzofurazan fluorophore (NBD) and at the upper rim with a thioether moiety has been synthesized and characterized by 1H NMR, 13C NMR, and mass spectrometry techniques. Both the absorption and emission spectral data for L in different solvents exhibited progressive changes with an increase in polarity. Ion recognition studies were performed by absorption and fluorescence spectroscopy using 10 different metal ions. Among these, Hg2+ exhibited greater changes in these spectra, whereas Cu2+ showed only significant changes and all other ions showed no change in the spectral features. Although the Hg2+ has dominant influence on the spectral features and provides a detection limit of 56.0 ± 0.6 ppb, the selectivity was hampered because of the presence of the derivatizations present on both the rims of L for ion interaction in solution. Therefore, L was immobilized onto gold nanoparticles (AuNPL’s) so that the upper rim derivatizations anchor o...