Through a topology guided strategy, a series of Zr6 containing isoreticular porphyrinic MOFs, PCN-228, PCN-229 and PCN-230, with ftw-a topology were synthesized using the elongated porphyrinic linkers. The highly conjugated porphyrin ring effectively prevents the network interpenetration which often appears in MOF structures with increased linker length. The pore aperture of the structures range from 2.5 nm to 3.8 nm and among them PCN-229 demonstrates the highest porosity and BET surface area among the previously reported Zr-MOFs. Additionally, by changing the relative direction of the terminal phenyl rings, this series replaces a Zr8 cluster with a smaller Zr6 cluster in a topologically identical framework. The high connectivity of the Zr6 cluster yields frameworks with enhanced stability despite high porosity and very long linker. As a representative example, PCN-230, constructed with the largest porphyrinic linker, shows excellent stability in aqueous solutions with pH values ranging from 0 to 12 and demonstrates one of the highest pH tolerances among all porphyrinic MOFs. This work not only presents a successful example of rational design of MOFs with desired topology, but also provides a strategy for the construction of stable mesoporous MOFs.

Topology guided design and syntheses of highly stable mesoporous porphyrinic zirconium MOFs with high surface areas

249th National Meeting (2015)

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