Fabrication of a two-dimensional bi-lanthanide metal-organic framework as a ratiometric fluorescent sensor based on...

Bimetallic lanthanide metal-organic frameworks (bi-Ln-MOFs) exhibit great appeal for ratiometric luminescent sensors due to their unique advantages. Specially, the low-lying energy of the empty 4f band of Ce⁴⁺ ions benefits Ce-MOFs with robust and broad fluorescent emission. Therefore, constructing ratiometric sensors based on Ce-MOFs is of significance but remains a challenge. Here, a two-dimensional (2D) bi-Ln-MOF is fabricated using Eu³⁺/Ce⁴⁺ and 5-boronoisophthalic acid (5-bop) via a crystal phase transformation strategy to construct a ratiometric luminescent Hg²⁺ sensor. Due to the lower energy gap of Ce⁴⁺ compared to Eu³⁺ and the corresponding stronger energy-absorption ability, the Ce⁴⁺ in bi-Ln-MOF shows a stronger and broader fluorescent emission than that of Eu³⁺. The substitution of the boric acid group in the bi-Ln-MOF by Hg²⁺ amplifies the difference between the two lanthanide ions. Therefore, the fluorescence intensity of Ce⁴⁺ increases whereas that of Eu³⁺ decreases accordingly, a behavior distinct from individual Eu-MOF or Ce-MOF performance. This novel bi-Ln-MOF sensor not only achieves a wide linear response range from 0.5 to 120 μM with a low detection limit of 167 nM for Hg²⁺, but also demonstrates exceptional selectivity and stability. The intriguing sensing mechanism of energy competition and the novel synthesis approach for 2D bi-Ln-MOF are anticipated to broaden the application possibilities of bi-Ln-MOFs for designing ratiometric sensors.