Stable Eu³⁺/Cu²⁺-Functionalized Supramolecular Zinc(II) Complexes as Fluorescent Probes for Turn-On and Ratiometric...

Fabrication of dual-emitting materials for H₂S sensing under environmental and biological conditions is currently of great interest. In this work, a new chemically stable metal supramolecular complex [Zn₂(pda)₂(H₂O)₃]·(H₂O)_0.5 (Znpda, pda = 1,10-phenanthroline-2,9-dicarboxylic acid), with accessible uncoordinated carboxylic oxygen sites, is solvothermally synthesized. It can serve as a host in luminescent hybrid composites. By incorporating Eu³⁺ and Cu²⁺ in the supramolecular coordination network, we obtained the dual-emitting hybrid material Eu³⁺/Cu²⁺@Znpda, which simultaneously shows intense ligand and weak Eu³⁺ emissions in HEPES buffer solution. Since H₂S can easily chelate with Cu²⁺ and recover the blocked "antenna effect" between the ligand and Eu³⁺, Eu³⁺/Cu²⁺@Znpda possesses both the turn-on and ratiomectric fluorescence response to H₂S. Accordingly, we designed an IMPLICATION logic gate for H₂S recognition by employing the fluorescence intensity ratio between the ligand and Eu³⁺ as the output signal. In addition, Eu³⁺/Cu²⁺@Znpda shows a fast response (<1 min) and high sensitivity (1.45 μM) to H₂S over other interfering species in the HEPES buffer solution, highlighting its potential use for H₂S sensing under environmental and biological conditions.