Stable terbium metal-organic framework with turn-on and blue-shift fluorescence sensing for acidic amino acids (L-aspartate and L-glutamine) and cations (Al3+ and Ga3+).

A terbium-based metal-organic framework, namely {[Tb2(ADIP)(H2ADIP)(HCOOH)(H2O)2]·2DMF·2H2O}n (Tb-MOF, H4ADIP = 5,5'-(anthracene-9,10-diyl) diisophthalic acid), was synthesized and characterized. The single-crystal structure analysis shows that the Tb-MOF crystallizes in the C2/C space group in the monoclinic system and its asymmetric unit contains two TbIII ions, one ADIP4-, one H2ADIP2-, one coordinating formic acid and two coordination water molecules. Tb-MOF has a three-dimensional porous structure with a porosity of 41.5%. Tb-MOF is a highly selective and sensitive fluorescence turn-on and blue-shift sensor for L-aspartate (Asp), L-glutamine (Glu), Al3+ and Ga3+with detection limits of 0.25, 0.23, 0.069 and 0.079 µM, respectively. Experimental studies and theoretical calculations show that the sensing process is mainly attributed to the energy transfer and the absorbance caused enhancement (ACE) mechanism. Therefore, Tb-MOF is a good multi-response fluorescence sensor for acidic amino acids and Al3+, Ga3+cations.

Anionic lanthanide metal-organic frameworks with magnetic, fluorescence, and proton conductivity properties and selective adsorption of a cationic dye.

Two novel microporous anionic lanthanide metal-organic frameworks (Ln-MOFs), namely {[(CH3)2NH2][Ln(bptc)]·2H2O}n (Ln = Gd (1) and Dy (2), H4bptc = biphenyl-3,3',5,5'-tetracarboxylic acid) with a new 4,8-connected topology have been synthesized and structurally characterized. Ln-MOF 1 shows a significant magnetocaloric effect with -ΔSmaxm = 26.37 J kg-1 K-1 at 2 K for ΔH = 7 T, and a high proton conductivity of 1.02 × 10-4 S cm-1 at 323 K and 90% RH. Moreover, Ln-MOF 1 shows specific selective adsorption of the cationic dye Rhodamine B. Ln-MOF 2 exhibits field-induced slow magnetic relaxation with an energy barrier (Ueff) of 48.19 K, characteristic emission of Dy3+, and selective adsorption of Rhodamine B. Therefore, 2 is a multifunctional Ln-MOF with magnetic, fluorescence and selective adsorption properties.