Abstract

A pyrene-based e xcited - state intramolecular proton transfer (ESIPT) active probe PMHMP was synthesized, characterized, and employed for the ppb-level, dual-mode, and high-fidelity detection of Cu2+ (LOD: 7.8 ppb) and Zn2+ ions (LOD: 4.2 ppb) in acetonitrile medium. The colorless solution of PMHMP turned yellow upon the addition of Cu2+, suggesting its ratiometric, naked-eye sensing. On the contrary, Zn2+ ions displayed concentration-dependent fluorescence rise till a 0.5 mole fraction and subsequent quenching. Mechanistic investigations indicated the formation of a 1:2 exciplex (Zn2+:PMHMP) at a lower concentration of Zn2+, which eventually turned into a more stable 1:1 (Zn2+:PMHMP) complex with an additional amount of Zn2+ ions. However, in both cases, it was observed that the hydroxyl group and the nitrogen atom of the azomethine unit were involved in the metal ion coordination, which eventually altered the ESIPT emission. Furthermore, a green-fluorescent 2:1 PMHMP-Zn2+ complex was developed and additionally employed for the fluorimetric analysis of both Cu2+ and H2PO4 - ions. The Cu2+ ion, owing to its higher binding affinity for PMHMP, could replace the Zn2+ ion from the preformed complex. On the other hand, H2PO4 - formed a tertiary adduct with the Zn2+-complex, leading to a distinguishable optical signal. Furthermore, extensive and organized density functional theory calculations were performed to explore the ESIPT behavior of PMHMP and the geometrical and electronic properties of the metal complexes.

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