Stable Lanthanide Metal-Organic Frameworks with Ratiometric Fluorescence Sensing for Amino Acids and Tunable Proton...

Four new isostructural lanthanide metal-organic frameworks (MOFs), namely {[Ln(DMTP-DC)_1.5(H₂O)₃]·DMF} [H₂DMTP-DC = 2',5'-dimethoxytriphenyl-4,4″-dicarboxylic acid; Ln^III = Eu^III (1), Gd^III (2), Tb^III (3), and Dy^III (4)], have been synthesized and characterized. Single-crystal structure analysis reveals that 1-4 are three-dimensional Ln-MOFs with rich H-bonding of coordinated H₂O molecules in the network channels. The X-ray diffraction patterns indicate that Ln-MOF 1 displays good stabilities in organic solvents and aqueous solutions with distinct pH values. Both 1 and 3 show characteristic emission of Ln^III ions. Ln-MOF 1 can be used as a ratiometric fluorescence sensor for arginine and lysine in aqueous solution, and the detection limits are 24.38 μM for arginine and 9.31 μM for lysine. All 1-4 show proton conductivity related to relative humidity (RH) and temperature, and the maximum conductivity values of 1-4 at 55 °C and 100% RH are 9.94 × 10^-5, 1.62 × 10^-4, 1.71 × 10^-4, and 2.67 × 10^-4 S·cm^-1, respectively. The value of σ increases with the decrease in ionic radius, indicating that the radius of the Ln^III ions can regulate the proton conductivity of these MOFs. Additionally, 2 exhibits a significant magnetocaloric effect (MCE) with a magnetic entropy change (-ΔS_m) of 18.86 J kg^-1 K^-1 for ΔH = 7 T at 2 K, and 4 shows weak field-induced slow relaxation of magnetization. The coexistence of good fluorescence sensing capability, attractive proton conductivity, and relatively large MCE in Ln-MOFs is rare, and thus, 1-4 are potentially multifunctional MOF materials.