A hetero-supermolecular-building-block strategy for the assembly of porous (3,12,24)-connected uru metal–organic frameworks

Supermolecular building block (SBB) approaches have been widely used for synthesizing highly connected metal–organic frameworks (MOFs). However, it remains a challenge to synthesize trinodal MOFs via SBB approaches. Here we report the assembly of (3,12,24)-connected uru-MOFs via a hetero-supermolecular-building-block (hetero-SBB) strategy, that is, using different types of highly connected metal–organic polyhedra (MOPs) as building units. This hetero-SBB strategy allows the facile synthesis of previously inaccessible uru-MOFs via 12-connected cuboctahedral and 24-connected rhombicuboctahedral MOPs. The uru-MOF-1, consisting of hierarchical microporous and mesoporous cages, exhibits a Brunauer–Emmett–Teller area of 3,170 m2 g−1. This MOF shows a high methane uptake of 339.6 cm3 (standard temperature and pressure) cm−3 at 159 K and 10 bar and is a promising candidate for low-temperature methane storage. The hetero-SBB strategy paves a way for the designed synthesis of highly connected MOFs, which are difficult to synthesize via traditional strategies, by taking advantage of the arsenal of synthetic MOPs. The synthesis of isoreticular (3,12,24)-connected uru metal–organic frameworks (MOFs) is reported by the assembly of 12-connected cuboctahedral and 24-connected rhombicuboctahedral supermolecular building blocks. The resulting uru-MOF-1 is a promising candidate for low-temperature methane storage.