“Turn-on” unsymmetrical azine based fluorophore for the selective detection of diethylchlorophosphate via photoinduced electron transfer to intramolecular charge transfer pathway

Abstract

The detection of chemical warfare agents (CWAs) in a highly selective, sensitive and speedy manner is essential for public safety in the case of terrorist attacks and achieving this is a challenging task. This study involves in developing a new unsymmetrical azine based fluorophore 4-((E)-(((E)-2-methoxybenzylidene)hydrazono)methyl)benzonitrile[A1] which shows high selectivity and sensitivity to the nerve agent mimic molecule, diethylchlorophosphate (DCP) through fluorescence switch on mechanism. In a fascinating manner, DCP sensing by A1 operates via solvent dependent optical output mechanisms. In the absence of DCP, the fluorescence of A1 was in the off state through photoinduced electron transfer process. In the presence of DCP, a nucleophilic substitution reaction occurs at the imine nitrogen is closer to the anisole moiety that results in the formation of a new intramolecular charge transfer state along with fluorescence enhancement. In acetonitrile, A1 shows 1763-fold fluorescence enhancement in the presence of DCP with a detection limit of 9.86 nM. In Acetonitrile/water (2:8) mixture, protonation at the imine nitrogen leads to 1188-fold fluorescence enhancement. The sensing mechanisms are confirmed by both experimental and time dependent density functional theoretical studies.