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 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 [Ru-3(CO)(12)], and the resulting {NUPF-1-RuCO} is catalytically active as a heterogeneous catalyst for intermolecular C(sp(3))-H amination. Excellent yields and good recyclability for amination of small substrates with various organic azides have been achieved.