Metal-Diamidobenzoquinone Frameworks via Post-Synthetic Linker Exchange,Journal of the American Chemical Society

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Metal-Diamidobenzoquinone Frameworks via Post-Synthetic Linker Exchange
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-02-04 , DOI: 10.1021/jacs.9b11952
Lujia Liu ₁ , Liang Li ₁ , Michael E Ziebel ₂ , T David Harris _{1,

2}

Affiliation

Metal-organic frameworks with amidic linkers often exhibit exceptional physical properties, but, owing to their strong metal-nitrogen bonds, are exceedingly challenging to isolate through direct synthesis. Here, we report a route to access metal-diamidobenzoquinone frameworks from their dihydroxobenzoquinone counterparts via post-synthetic linker exchange. The parent compounds (Me2NH2)2[M2L3] (M = Zn, Mn; H2L = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinone) under-go linker exchange upon exposure to a solution of deprotonated 2,5-diamino-3,6-dibromo-1,4-benzoquinone or 2,5-diamino-3,6-dichloro-1,4-benzoquinone, proceeding through crystal-to-single-crystal reactions. The presence of both types of linker in the resulting frameworks is confirmed by a combination of NMR, Raman, and energy-dispersive X-ray (EDX) spectroscopies. Moreover, the extent of linker exchange in the Zn frameworks is quantified using 13C NMR spectroscopy, and spatially-resolved EDX spectroscopy reveals the two types of linker to be homogenously distributed within a crystal. This work provides the first method to exchange organic linkers with different donor atoms in metal-organic frameworks, and it offers a potential synthetic pathway toward new materials with exotic metal-linker coordination modes.

中文翻译：

通过合成后接头交换的金属-二酰氨基苯醌框架

带有酰胺键的金属-有机骨架通常表现出特殊的物理性质，但由于其强大的金属-氮键，通过直接合成分离非常具有挑战性。在这里，我们报告了一种通过合成后接头交换从其二羟基苯醌对应物获得金属-二氨基苯醌框架的途径。母体化合物 (Me2NH2)2[M2L3]（M = Zn, Mn；H2L = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinone）在暴露于去质子化 2 ,5-diamino-3,6-dibromo-1,4-benzoquinone 或 2,5-diamino-3,6-dichloro-1,4-benzoquinone，通过晶体到单晶的反应进行。通过 NMR、拉曼和能量色散 X 射线 (EDX) 光谱的组合证实了所得框架中两种类型的接头的存在。而且，使用 13C NMR 光谱对 Zn 骨架中的接头交换程度进行量化，并且空间分辨 EDX 光谱显示两种类型的接头均匀分布在晶体内。这项工作提供了第一种在金属 - 有机骨架中与不同供体原子交换有机连接体的方法，并为具有奇异金属 - 连接体配位模式的新材料提供了潜在的合成途径。

更新日期：2020-02-04

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