Dual-Mode Multiple Ion Sensing via Analyte-Specific Modulation of Keto-Enol Tautomerization of an ESIPT Active Pyrene...

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.