The
last few decades witnessed a remarkable advancement in the
field of molecular anion receptors. A variety of anion binding motifs
have been discovered, and large number of designer molecular anion
receptors with high selectivity are being reported. However, anion
detection in an aqueous medium is still a formidable challenge as
evident from only a miniscule of synthetic systems available in the
literature. We, herein, report 5,5′-dithio-bis(2-nitrobenzoic
acid) (Ellman’s reagent) appended with amino acids as supersensitive
anion sensors that can detect F– and H2PO4
– ions in both aqueous as well as
organic media. Interestingly, the sensors showed a dual response to
anions, viz., chromogenic response in organic medium and electrochemical
response in aqueous solutions. Various spectroscopic techniques such
as UV–vis and 1H NMR are used to investigate the
binding studies in acetonitrile, whereas electrochemical methods such
as cyclic voltammetry (CV) and differential pulse voltammetry (DPV)
are employed to explore the anion binding in water. The host–guest
complex stoichiometry and binding constants are calculated using the
BindFit software. The geometry of host–guest complex has been
optimized by the density functional theory (DFT) method. These molecules
are versatile sensors since these function in both water and acetonitrile
with extremely low limit of detection (LOD) up to 0.07 fM and limit
of quantification (LOQ) up to 0.23 fM. To our knowledge, the present
system is the first example of a sensor that can detect the lowest
concentration of anions in water quantitatively. The minimalistic
design strategy presented here opens up the innumerable possibilities
for designing dual anion sensors in a one fell swoop.