Lanthanide-Based Metal-Organic Frameworks Containing "V-Shaped" Tetracarboxylate Ligands: Synthesis, Crystal Structures, "Naked-Eye" Luminescent Detection, and Catalytic Properties.

Three lanthanide-based metal-organic frameworks, [Tb(HMDIA)(H2O)3]·H2O (Tb-MDIA), [Ho(HMDIA)(H2O)3]·(H2O)2 (Ho-MDIA), and [Nd(HMDIA)(H2O)3]·(H2O)2 (Nd-MDIA) from the same V-shaped ligand 5,5'-methylenediisophthalic acid (H4MDIA), were prepared by mixing Ln3+ and H4MDIA under solvothermal conditions. The crystal structures of the three complexes were determined by single-crystal X-ray diffraction. The different coordination modes of the organic ligands resulted in different framework structures among the three complexes. The luminescent properties of Ln-MDIA in the ultraviolet-visible region were also studied. Interestingly, the bright-green emitter Tb-MDIA showed high selectivity and sensitivity to allow the naked-eye visualization of Fe3+ ions and picric acid (PA) explosive, and both sensing mechanisms were revealed. Finally, Ho-MDIA and Nd-MDIA were shown to work as heterogeneous catalysts for the cyanosilylation reaction of aromatic aldehydes, and the catalysts could be recycled at least three times without any decrease in activity.