Selective Detection of Trinitrophenol by Amphiphilic Dimethylaminopyridine-Appended Zn(II)phthalocyanines at the Near-Infrared Region.

Novel amphiphilic Zn(II)phthalocyanines (ZnPcs) peripherally substituted with four and eight dimethylaminopyridinium units (ZnPc and ZnPc) were synthesized by cyclotetramerization of the corresponding phthalonitriles. The effect of aggregation and photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties was investigated. The chemosensing ability of ZnPcs toward explosive nitroaromatic compounds was explored in aqueous medium. This study demonstrates that ZnPc and ZnPc show fluorescence quenching behavior upon interaction with different nitro analytes and show unprecedented selectivity toward 2,4,6-trinitrophenol with a limit of detection (LOD) of 0.7-1.1 ppm with a high quenching rate constant ( ) of 1.6-2.02 × 10. The near-infrared (NIR) fluorescence in thin films was quenched efficiently because of the photoinduced electron-transfer process through strong intermolecular π-π and electrostatic interactions. The sensing process is highly reversible and free from the interference of other commonly encountered nitro analytes. Further, experiments were performed to demonstrate the use of ZnPcs as efficient heterogeneous photocatalysts in the reduction of nitro explosives. The smart dual performance of multicharged ZnPcs in aqueous media quantifies them as attractive candidates in developing sensor materials at the NIR region and to possibly convert the toxic explosives into useful scaffolds. These results provide an interesting perspective toward elaboration of stable fluorescent systems for the selective sensing behavior of nitro explosives and their facile heterogeneous catalytic behavior in the reduction reactions.