Metal-Organic Frameworks (MOFs) have gained a tremendous amount of attention in the past few decades. Due to the tunable nature of their ligand geometry, their enormous surface area and their large gas uptake capacities, MOFs are widely applied in many areas such as gas storage, gas separation, CO2 capture, catalysis, drug delivery, sensors, photosensitive materials and magnetic materials. However; rational design of MOFs with desired characteristics still remains largely challenging. A careful inspection of the framework topology from the atomic level may provide a novel insight to the rational design of MOFs. In this work, we have demonstrated a successful implementation of symmetry-guided design of stable, non-interpenetrated MOFs with the expected topology from the atomic level, and reported a series of isoreticular MOFs with high porosity, large stability and desired topology. In particular, PCN-521 possesses the largest cavity size (20.5 � 20.5 � 37.4 �), BET surface area (4040 m2 g-1) and solvent accessible volume (78.50%) among all the published MOFs from tetrahedral ligands. Second, it is the first examples of non-interpenetrated MOFs synthesized from the MTBC ligand. Third, it is the first example of Zr MOFs constructed from tetrahedral ligands.The successful synthesis of PCN-521 has provided a general way of making stable, non-interpenetrated MOFs with large porosities. New structures can be obtained by varying both the organic linkers and the metal SBUs. An isostructural MOF, PCN-523, was obtained by replacing the 8-connected Zr clusters with Hf clusters. This Hf MOF also possesses a high chemical and thermal stability. Due to the non-interpenetrated nature of fluorite-topology framework, it is suggested that a further elongation of the tetrahedral ligands may result in MOFs with even larger cavities. PCN-524 was obtained by combining the Zr clusters with a further elongated tetrahedral ligand. It possesses a cavity size of 22.8 � 22.8 � 40.2 �. This work not only illustrates a successful case of designing MOFs with a desired topology from the atomic level, but also provides a systematic way to construct stable, non-interpenetrated MOFs with large porosities.References:Zhang, M.; Chen, Y.-P.; Bosch, M.; Gentle, T.; Wang, Z. U.; Zhou, H.-C., Angew. Chem. Int. Ed. 2013  , ASAP: 10.1002/anie.201307340Zhang, M.; Chen, Y.-P.; Zhou, H.-C., CrystEngComm. 2013  , ASAP: 10.1039/C3CE41105BZhang, M.; Chen, Y.-P.; Bosch M.; Sun, Y.; Gentle, T.; Zhou, H.-C., J. Am. Chem. Soc. 2014  , manuscript in preparation

Symmetry-guided synthesis of highly porous metal-organic frameworks with desired topology for clean energy applications

247th National Meeting (2014)

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