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J Am Chem Soc. 2019 Feb 20;141(7):3129-3136. doi: 10.1021/jacs.8b12530. Epub 2019 Feb 8.

Tuning the Ionicity of Stable Metal-Organic Frameworks through Ionic Linker Installation.

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Department of Chemistry , Texas A&M University , College Station , Texas 77843-3255 , United States.
State Key Laboratory of Structure Chemistry , Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou , Fujian 350002 , China.
University of Chinese Academy of Sciences , Beijing 100049 , China.


The predictable topologies and designable structures of metal-organic frameworks (MOFs) are the most important advantages for this emerging crystalline material compared to traditional porous materials. However, pore-environment engineering in MOF materials is still a huge challenge when it comes to the growing requirements of expanded applications. A useful method for the regulation of pore-environments, linker installation, has been developed and applied to a series of microporous MOFs. Herein, employing PCN-700 and PCN-608 as platforms, ionic linker installation was successfully implemented in both microporous and mesoporous Zr-based MOFs to afford a series of ionic frameworks. Selective ionic dye capture results support the ionic nature of these MOFs. The mesopores in PCN-608 are able to survive after installation of the ionic linkers, which is useful for ion exchange and further catalysis. To illustrate this, Ru(bpy)32+, a commonly used photoactive cation, was encapsulated into the anionic mesoporous PCN-608-SBDC via ion exchange. Photocatalytic activity of Ru(bpy)3@PCN-608-SBDC was examined by aza-Henry reactions, which show good catalytic performance over three catalytic cycles.


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