Synthesis and photophysical properties of 3-aryl-2-cyanoacrylamides: Design of a turn-on fluorescent probe for cyanide ion detection

Abstract

Three 3-aryl-2-cyanoacrylamide derivatives were synthesised in 71−79 % yields from cheap reagents and mild reaction conditions using the Et3N-mediated Knoevenagel condensation of fluorescent arylaldehydes (e.g., triphenylamine and anthracene) with cyanoacetamide. These dyes' photophysical properties and anions-recognizing behaviour were studied, revealing that the 9-anthracenyl derivative can "turn on" fluorescence in cyanide presence, with high selectivity and a detection limit (LOD) of 710 nM. Initially, there is fluorescence quenching by the energy transfer (ET) from the anthracene ring to the 2-cyanoacrylamide moiety due to the non-coplanarity of these fragments and, upon the cyanide addition to Cβ of the receptor unit, the intrinsic fluorescence of anthracene is restored. HRMS and NMR experiments and TD-DFT calculations were performed to confirm the detection mechanism and fluorescence properties of the design chemodosimeter; fluorescent test paper was also used to detect cyanide in an aqueous medium.