An interesting aggregation induced red shifted emissive and ESIPT active hydroxycoumarin tagged symmetrical azine: Colorimetric and fluorescent turn on-off-on response towards Cu2+ and Cysteine, real sample analysis and logic gate application.

Abstract

We report a newly synthesized 7-diethylamino-4-hydroxycoumarin tagged symmetrical azine derivative (SHC), with an interesting color transformation from yellowish green to orange via aggregation induced red shifted emissive (117 nm) feature in THF-H₂O mixture. Interestingly, the single crystal X-ray analysis of this molecule demonstrates that two hydroxycoumarin moieties were present in azine unit, among them one of the coumarin units was exist as enol form and another one transferred to keto form via ground state proton transfer reaction. The optical responses of the compound in different solvents exposed the observation of dual emissive bands which corresponds to the presence of ESIPT phenomenon in SHC molecule. Further, this characteristic was confirmed by absorption, emission, solid state structure and time resolved fluorescence decay measurements. Furthermore, the fluorophore, SHC was exploited as a colorimetric and turn on-off-on fluorescent probe for detection of Cu²⁺ ions and Cysteine (Cys). The 1:1 binding ratio of the probe with Cu²⁺ and Cys with SHC-Cu²⁺, was established via Job plot analysis, mass spectral technique and the DFT calculations. The probe, SHC was employed for the detection of copper ions in the environmental real water samples. Finally, the reversible fluorescent turn on-off-on character of the probe, SHC was established to construct the IMPLICATION logic gate application.