Chemical Conversion of Linkages in Covalent Organic Frameworks
Chemical Conversion of Linkages in Covalent Organic Frameworks
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DOI：
10.1021/jacs.6b08377
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发表时间：
2016-12-07
影响因子：
15
通讯作者：
Yaghi, Omar M.
中科院分区：
文献类型：
--
作者：
Waller, Peter J.;Lyle, Steven J.;Yaghi, Omar M.
两个层状多孔共价有机框架（COF）的亚胺键，TPB-TP-COF（[C6H3（C6H4N）（3）]（2）[C6H4（CH）（2）]（3），1）和4PE-1P-COF（[C-2（C6H4N）（4）][C6H4（CH）（2）]（2），2），已转化为酰胺键，以通过直接氧化制备相应的同构酰胺COF 1'和2'，同时保留结晶度和永久孔隙率。值得注意的是，如通过FT-IR和C-13 CP-MAS NMR光谱所评估的，两种亚胺COF的氧化都是完全的，并且证明了（a）COF键的第一次化学转化和（B）如何可以绕过COF化学中遇到的通常的“结晶问题”以获得通常被认为难以通过通常的从头方法获得的COF，例如这些酰胺。酰胺COF相对于它们的亚胺前体显示出改善的化学稳定性。
The imine linkages of two layered, porous covalent organic frameworks (COFs), TPB-TP-COF ([C6H3(C6H4N)(3)](2)[C6H4( CH)(2)](3), 1) and 4PE-1P-COF ([C-2(C6H4N)(4)][C6H4(CH)(2)](2), 2), have been transformed into amide linkages to make the respective isostructural amide COFs 1' and 2' by direct oxidation with retention of crystallinity and permanent porosity. Remarkably, the oxidation of both imine COFs is complete, as assessed by FT-IR and C-13 CP-MAS NMR spectroscopy and demonstrates (a) the first chemical conversion of a COF linkage and (b) how the usual "crystallization problem" encountered in COF chemistry can be bypassed to access COFs, such as these amides, that are typically thought to be difficult to obtain by the usual de novo methods. The amide COFs show improved chemical stability relative to their imine progenitors.