Copper(II) pseudoatrane 附加异质双金属 2D-MOF：一种具有催化和传感性能的多功能材料,Applied Organometallic Chemistry

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Copper(II) pseudoatrane 附加异质双金属 2D-MOF：一种具有催化和传感性能的多功能材料
Applied Organometallic Chemistry ( IF 3.7 ) Pub Date : 2023-03-22 , DOI: 10.1002/aoc.7083
Agrima Datta ₁ , Mamta Guleria ₂ , Keshav Kumar ₂ , Jyoti Agarwal ₂ , Raghubir Singh ₁ , Varinder Kaur ₂

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_{采用新型三足配体 N{CH 2} COOH} ₂ {CH ₂ (2- t -Bu-4-CH ₃ -C ₆ H ₂ -OH)}构建了首个二维杂双金属 MOF ( 2 ) （1）。单晶 X 射线衍射描绘了 [4.3.3.0 ^1,5] pseudoatrane 笼，其中铜 (II) 离子达到三角双锥几何形状。此外，共存的钠（I）离子获得了由甲醇分子和配体的游离羧酸盐位点产生的五角双锥形几何结构。该化合物是同类化合物中的第一个，其中铜 (II) 伪杂环烷笼和七配位钠离子的顺序结合产生了具有片状结构的异双金属金属有机骨架。具有高达 250°C 稳定性的 MOF 的 TEM 和 SEM 图像显示了具有花状形态的球形结构（~78 nm）的形成。异质双金属 2D-MOF 被证明是一种多功能材料，因为它成功地催化了 Friedel-Craft' s 吲哚与 β-硝基苯乙烯的烷基化反应，以及通过分光光度法和比色法研究有效检测有毒溴化阻燃剂。值得注意的是，使用 DCM 作为溶剂可以看到最好的催化效果，而 2-甲基吲哚与 2-Br- 反应得到的烷基化产物β-硝基苯乙烯的产率高达 98%。此外，2D-MOF 显示出对五溴苯酚和四溴邻苯二甲酸酐的选择性响应，在添加 TBPA 时峰发生猝灭，而使用 PBP 观察到峰从 457 nm 移动到 402 nm。通过将 MOF 成功地结合到用于 BFR 现场检测的便携式硅胶条中，探索了 MOF 的实际应用。

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Copper(II) pseudoatrane appended heterobimetallic 2D-MOF: A multi-functional material with catalytic and sensing properties

A maiden two-dimensional atrane-based heterobimetallic MOF (2) was constructed employing a novel tripodal ligand N{CH₂COOH}₂{CH₂(2-t-Bu-4-CH₃-C₆H₂-OH)} (1). Single-crystal X-ray diffraction depicted the formation of [4.3.3.0^1,5] pseudoatrane cage in which copper(II) ions attained trigonal bipyramidal geometry. Besides, the co-existing sodium(I) ions acquired a pentagonal bipyramidal geometry produced by methanol molecules and free carboxylate sites of the ligand. This compound is the first of its kind where the sequential binding of copper(II) pseudoatrane cage and hepta-coordinated sodium ion generated a heterobimetallic metal–organic framework with a sheet-like structure. The TEM and SEM images of the MOF having stability up to 250°C revealed the formation of spherical structures (~78 nm) with flower-like morphology. The heterobimetallic 2D-MOF was proved to be a multifunctional material as it successfully catalysed Friedel–Craft's alkylation of Indole with beta-nitrostyrene as well as utilised for the efficient detection of toxic brominated flame retardants through spectrophotometric and colorimetric studies. Remarkably, the best catalysis results were seen using DCM as a solvent, and the alkylation product obtained from the reaction of 2-methylindole with 2-Br-β-nitrostyrene showed an extraordinary yield of 98%. Besides, the 2D-MOF showed a selective response with pentabromophenol, and tetrabromophthalic anhydride with quenching in peak on the addition of TBPA while shifting of the peak was observed from 457 to 402 nm with PBP. The practical application of the MOF was explored by its successful incorporation into portable silica strips for on-the-spot detection of BFRs.

更新日期：2023-03-22

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