Spectroscopic and TD-DFT studies on the chromo-fluorogenic detection of cyanide ions in organic and aquo-organic media.

ABSTRACT

A new naked-eye chromogenic and fluorogenic probe KS5 has been developed for the detection of CN- ions in neat DMSO and H2ODMSO (11 v/v) media. The probe KS5 exhibited selectivity towards CN- and F- ions in organic and high selectivity towards CN- ions in aquo-organic media resulting in a colour change from brown to colourless and a turn-on fluorescence response. The probe could able to detect CN- ions via a deprotonation process, which was conceived by consecutive addition of hydroxide and hydrogen ions and confirmed using 1H NMR studies. The limit of detection (LOD) of KS5 towards CN- ions were in the range of 0.07-0.62 µM in both these solvent systems. Suppression of intra-molecular charge transfer (ICT) transition and photoinduced electron transfer (PET) process of KS5 by the added CN- ions are responsible for the chromogenic and fluorogenic changes observed, respectively. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) calculations strongly supported the proposed mechanism along with the optical properties of the probe before and after the addition of CN- ions. To prove the practical applicability, KS5 was successfully utilized to detect CN- ions in cassava powder and bitter almonds as well as to determine CN- ions in various real water samples.