American Chemical Society
ja8b02710_si_001.pdf (2.64 MB)

Tailor-Made Pyrazolide-Based Metal–Organic Frameworks for Selective Catalysis

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journal contribution
posted on 2018-05-02, 00:00 authored by Ning Huang, Kecheng Wang, Hannah Drake, Peiyu Cai, Jiandong Pang, Jialuo Li, Sai Che, Lan Huang, Qi Wang, Hong-Cai Zhou
The predesignable porous structures in metal–organic frameworks (MOFs) render them quite attractive as a host–guest platform to address a variety of important issues at the frontiers of science. In this work, a perfluorophenylene functionalized metalloporphyrinic MOF, namely, PCN-624, has been rationally designed, synthesized, and structurally characterized. PCN-624 is constructed by 12-connected [Ni8(OH)4(H2O)2Pz12] (Pz = pyrazolide) nodes and fluorinated 5,10,15,20-tetrakis­(2,3,5,6-tetrafluoro-4-(1H-pyrazol-4-yl)­phenyl)-porphyrin (TTFPPP) linker with an ftw-a topological net. Notably, PCN-624 exhibits extinguished robustness under different conditions, including organic solvents, strong acid, and base aqueous solutions. The pore surface of PCN-624 is decorated with pendant perfluorophenylene groups. These moieties fabricate densely fluorinated nanocages resulting in the selective guest capture of the material. More importantly, PCN-624 can be employed as an efficient heterogeneous catalyst for the selective synthesis of fullerene–anthracene bisadduct. Owing to the high chemical robustness of PCN-624, it can be recycled over five times without significant loss of its catalytic activity. All of these results demonstrate that MOFs can serve as a powerful platform with great flexibility for functional design to solve various synthetic problems.