A Quest for Parsimonious Topology of Polyhedral Cavities in Metal–Organic Frameworks

A new topology previously unknown in metal–organic frameworks (MOFs) provides an important clue to uncovering a new series of polyhedral MOFs. We report a novel MOF crystallized in a parsimonious mep topology based on Frank–Kasper (FK) polyhedra. The distribution of angles in a tetrahedral arrangement (T-O-T) is crucial for the formation of FK polyhedra in mep topology. This finding led us to investigate the T-O-T angle distribution in related zeolites and zeolitic imidazolate frameworks (ZIFs). Unlike zeolites, it is extremely difficult to achieve high T-O-T angles in ZIFs, which prevents the formation of some FK topologies. Density functional theory (DFT) total energy calculations support a correlation between T-O-T angles and the feasibility of new tetrahedron-based FK frameworks. This result may lead to innovative ways of accessing new cellular topologies by simple chemical tweaking of T-O-T angles.