Highly Stable Mesoporous Zirconium Porphyrinic Frameworks with Distinct Flexibility

The construction of highly stable metal–porphyrinic frameworks (MPFs) is appealing as these materials offer great opportunities for applications in artificial light‐harvesting systems, gas storage, heterogeneous catalysis, etc. Herein, we report the synthesis of a novel mesoporous metal–porphyrinic...

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Bibliographic Details
Published in:Chemistry : a European journal 2016-04, Vol.22 (18), p.6268-6276
Main Authors: Xu, Lei, Luo, Yan-Ping, Sun, Lin, Xu, Yan, Cai, Zhong-Sheng, Fang, Min, Yuan, Rong-Xin, Du, Hong-Bin
Format: Article
Language:English
Subjects:
Catalysis
Catalysts
Chemistry
Flexibility
heterogeneous catalysis
mesoporous materials
metal-organic frameworks
Metalorganic compounds
Porphyrins
Recyclability
Thermal stability
Zirconium
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Summary:The construction of highly stable metal–porphyrinic frameworks (MPFs) is appealing as these materials offer great opportunities for applications in artificial light‐harvesting systems, gas storage, heterogeneous catalysis, etc. Herein, we report the synthesis of a novel mesoporous metal–porphyrinic framework (denoted as NUPF‐1) and its catalytic properties. NUPF‐1 is constructed from a new porphyrin linker and a Zr6O8 structural building unit, possessing an unprecedented doubly interpenetrating scu net. The structure exhibits not only remarkable chemical and thermal stabilities, but also a distinct structural flexibility, which is seldom seen in metal–organic framework (MOF) materials. By the merit of high chemical stability, NUPF‐1 could be easily post‐metallized with [Ru3(CO)12], and the resulting {NUPF‐1–RuCO} is catalytically active as a heterogeneous catalyst for intermolecular C(sp3)−H amination. Excellent yields and good recyclability for amination of small substrates with various organic azides have been achieved. Flexible but firm: A mesoporous metal–porphyrinic framework, named NUPF‐1, was synthesized, which possesses an unprecedented doubly interpenetrated scu framework. NUPF‐1 exhibits not only exceptionally high chemical and thermal stabilities, but also a distinct structural flexibility. After post‐metallization with [Ru3(CO)12], the resulting structure could be used as a heterogeneous C(sp3)−H amination catalyst.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201600447