A reaction-based carbazole-dicyanovinyl conjugated colorimetric and ratiometric fluorescent probe for selective detection of cyanide ions

Abstract

In the present work, 4-(9'-hexylcarbazol-3'-yl)benzylidenemalononitrile 5 (probe L) was tested as a colorimetric and ratiometric fluorescent probe in dimethyl sulfoxide (DMSO) medium towards anions, cations and neutral molecules. The sensing properties of probe L were investigated by using UV-Vis absorption and fluorescence spectroscopy techniques. Probe L showed selectivity and sensitivity towards cyanide ions (CN-) in the presence of analytes used. Upon the addition of CN-, intramolecular charge transfer (ICT) band at 425 nm in UV spectrum disappeared. In addition, ICT emission intensity at 593 nm decreased and ligand-centred (LC) emission intensity at 480 nm increased. These findings indicate that nucleophilic conjugate addition of CN- to the dicyanovinyl group of probe L successfully occurs, hence forming a new adduct between probe L and CN-. In this adduct, pi-conjugation was partially blocked, and the ICT transfer was hindered. Adduct formation was proved by Job's plot, H-1 NMR and FT-IR analysis. Probe L showed very low limit of detection (LOD) value of 1.467 nM towards CN-. Probe L was also applied to the CN- detection in real-world water samples by the spike and recovery method. The maximum relative standard deviation (RSD) value was 4.24, indicating this method works successfully. Therefore, probe L could find a potential use in detection of CN- in liquid media.