Post-Synthetic Modification of Metal–Organic Framework Thin Films Using Click Chemistry: The Importance of Strained C–C Triple Bonds

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• 作者：Zhengbang Wang ; Jinxuan Liu ; Hasan K. Arslan ; Sylvain Grosjean ; Tobias Hagendorn ; Hartmut Gliemann ; Stefan Br?se ; Christof W?ll
• 刊名：Langmuir
• 出版年：2013
• 出版时间：December 23, 2013
• 年：2013
• 卷：29
• 期：51
• 页码：15958-15964
• 全文大小：362K
• ISSN：1520-5827

文摘

In this work, we demonstrate that strain-promoted azide鈥揳lkyne cycloaddition (SPAAC) yields virtually complete conversion in the context of the post-synthetic modification (PSM) of metal鈥搊rganic frameworks (MOFs). We use surface-anchored MOF (SURMOF) thin films, [Zn₂(N₃-bdc)₂(dabco)], grown on modified Au substrates using liquid-phase epitaxy (LPE) as a model system to first show that, with standard click chemistry, presently, the most popular method for rendering additional functionality to MOFs via PSM, quantitative conversion yields, cannot be reached. In addition, it is virtually impossible to avoid contaminations of the product by the cytotoxic Cu^I ions used as a catalyst, a substantial problem for applications in life sciences. Both problems could be overcome by SPAAC, where a metal catalyst is not needed. After optimization of reaction conditions, conversion yields of nearly 100% could be achieved. The consequences of these results for various applications of PSM-modified SURMOFs in the fields of membranes, optical coatings, catalysis, selective gas separation, and chemical sensing are briefly discussed.