Lanthanide Antenna Amplifier Multiplies the Optical Sensing Efficiency in Phototautomeric Metal–Organic Frameworks

Metal-organic frameworks (MOFs) incorporating phototautomeric ligands have shown significant potential for new-generation optical sensing devices. It is challenging to enlarge the energy difference of tautomers, which is crucial for improving the sensing efficiency. Herein, we report a novel tactic to amplify the excited-state intramolecular proton transfer (ESIPT) effect via the "antenna effect" in lanthanide sensitization. Specifically, by leveraging the enol (E)-keto (K) phototautomerization process, we achieve precise manipulation of the energy gap between the lowest ligand triplet state and the Eu(III) emitting level through fine-tuning. As a result, the small wavelength shift (10 nm) between the E* and K* emissions is amplified into an approximately 65-fold intensity change in Eu(III) emission. This enhancement is accompanied by a significantly lowered limit of detection (LOD: 0.53 μg/L) and improved sensitivity (0.6955% RH^-1) in real-time humidity monitoring across a broad linear detection range (0-95.0% RH). Computational simulations and single-crystal analyses demonstrate two key mechanisms: (1) the appropriate hydrophilic/hydrophobic distribution in the MOF cavity facilitates rapid hydration/dehydration and (2) H₂O desorption/adsorption-dependent ESIPT switching governs the deactivation/activation of the Eu(III) 4f excited state. This work presents an optimization approach to enhance energy utilization in MOF-based optical sensing.