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基于巴比妥酸二羧酸官能化芳基腙的镧系金属有机骨架:合成、结构、发光及醛的氰硅烷化催化作用。

Lanthanide metal organic frameworks based on dicarboxyl-functionalized arylhydrazone of barbituric acid: syntheses, structures, luminescence and catalytic cyanosilylation of aldehydes.

机构信息

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001, Lisbon, Portugal.

出版信息

Dalton Trans. 2017 Jul 4;46(26):8649-8657. doi: 10.1039/c7dt01056g.

Abstract

Five isostructural lanthanide MOFs, [Ln(1κOO',2κO'',3κO''',4κO''''-μ-L)(NO)(DMF)]·n(DMF) {Ln = La (1), Ce (2), Nd (3), Sm (4) and Dy (5); L = 5-[2-{2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene}hydrazinyl]isophthalate; DMF = N,N'-dimethyl formamide}, based on dicarboxyl-functionalized arylhydrazone of barbituric acid were synthesized under solvothermal conditions. They were characterized by elemental analysis, FT-IR spectroscopy, thermogravimetric and X-ray diffraction analyses. Crystal structure analysis revealed that these frameworks possess a similar type of two dimensional (2D) structure with a dinuclear {Ln(COO)} unit acting as a secondary building block. Topological analysis shows that these frameworks display a 3,6-connected kgd; Shubnikov plane (3.6.3.6)/dual net. They exhibit excellent heterogeneous catalytic activities (compound 2 is the most active one) towards the cyanosilylation of aldehydes under solvent-free conditions. These catalysts can be recycled at least up to five cycles without a loss of activity. Compounds 1-5 exhibit luminescence properties in the solid state at room temperature.

摘要

五种同构的镧系 MOFs,[Ln(1κOO',2κO'',3κO''',4κO''''-μ-L)(NO)(DMF)]·n(DMF) {Ln = La (1), Ce (2), Nd (3), Sm (4) and Dy (5); L = 5-[2-{2,4,6-三氧代六氢嘧啶-5(2H)-亚基}肼基]间苯二甲酸;DMF = N,N'-二甲基甲酰胺},是基于巴比妥酸的二羧酸官能化芳基腙在溶剂热条件下合成的。它们通过元素分析、FT-IR 光谱、热重和 X 射线衍射分析进行了表征。晶体结构分析表明,这些骨架具有相似类型的二维(2D)结构,其中双核{Ln(COO)}单元作为次级构筑块。拓扑分析表明,这些骨架显示出 3,6-连接的 kgd;Shubnikov 平面(3.6.3.6)/对偶网络。它们在无溶剂条件下对醛的氰硅烷化表现出优异的多相催化活性(化合物 2 是最活跃的)。这些催化剂可以至少循环使用五次而不会失去活性。化合物 1-5 在室温下在固态下表现出发光性质。

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