Syntheses, Crystal Structures and Properties of Metal-organic Frameworks of Lanthanide Metals with 4,4‘,4‘‘-s-Triazine-1,3,5-triyltri-p-aminobenzoate as Triangular Organic Linkers

• Main Authors: Chien-Yuan Lai, 賴建元
• Other Authors: Ju-Hsiou Liao
• Format: Others
• Language: zh-TW
• Published: 2013
• Online Access: http://ndltd.ncl.edu.tw/handle/22969979645977794777

碩士 === 國立中正大學 === 化學暨生物化學研究所 === 101 === Here we report that the self-assembly of lanthanide ions with carboxylate-based organic ligands, such as 4,4',4''-s-Triazine-1,3,5-triyltri-p-aminobenzoate (H3TATAB) afforded thirteen novel metal-organic frameworks (MOFs) under solvothermal conditions : [Y(TATAB)(DMA)3]•H2O (1), [La(TATAB)(DMSO)2]•2DMSO (2), [Ln2(TATAB)2(H2O)(DMA)6] {Ln = La (3), Pr (4), Nd (5)}, [Ln2(TATAB)2(H2O)(DMA)6]•5H2O {Ln = Sm (6), Eu (7), Gd (8), Tb (9), Dy (10), Er (11), Tm (12), Yb (13)}. Single-crystal X-ray diffraction studies indicate (3), (4), (5) are isostructures, and (6) to (13) are also isostructures, all of them are 3-dimensional frameworks. Among these compounds, pore volume ratio of compound (2) is 39.8%. The solvent accessible free volumes of (6) to (13), calculated by PLATON, are approximately 51% of the crystal volume. The structure of (1) to (13), appear to collapse into amorphous phases upon the removal of solvent molecules were studied by thermal analyses and powder X-ray diffraction. [Ln2(TATAB)2(H2O)(DMA)6]•5H2O {Ln = Sm(6), Eu(7), Tb(9), Dy(10)} have photoluminescent properties, which show Ln3+ characteristic emission, and their luminescent properties are also investigated. Compounds (7), (9) exhibit intense characteristic lanthanide emissions, as a result of antenna effect.