AIE Ligand-Based Luminescent Ln-MOFs for Rapid and Selective Sensing of Tetracycline

The design of highly stable and dual-emission lanthanide metal-organic frameworks (Ln-MOFs) is promising for practical chemical sensor applications. Rational design and synthesis of photoresponsive organic ligands provide a feasible approach to achieving highly fluorescent dual-emission Ln-MOFs. In this study, a tetraphenylpyrazine-based AIE ligand, H₄L, was synthesized and combined with lanthanide ions (including Sm³⁺, Eu³⁺, Gd³⁺, and Tb³⁺) to fabricate a series of Ln-MOFs named Ln-L. The single-crystal analysis revealed that all Ln-L belonged to the tetragonal space group P42₁2 and featured a 2-fold interpenetrated 3D structure. Leveraging rational design, Eu-L exhibited a sensitive response to tetracycline, making it a promising fluorescence sensor for tetracycline detection. The experiments demonstrated that Eu-L could rapidly and quantitatively detect tetracycline and its analogs within 30 s. The lowest detection limits for tetracycline, oxytetracycline, and chlortetracycline were 0.43, 0.92, and 0.81 μM, respectively. Additionally, the probe displayed excellent reusability and exceptional selectivity. A plausible sensing mechanism was proposed, supported by both experimental and theoretical analyses. Furthermore, the study discovered that on-site and real-time determination of TCs in aqueous solutions could be achieved by using luminescence test papers and composite films derived from Eu-L.