The chemistry of metal–organic frameworks with face-centered cubic topology

The precise control of molecular building blocks (MBBs) permits access to various types of tailor-made functional materials. The best example of this is in the assembly of metal–organic frameworks (MOFs) comprising many types and arrangements of pre-designed organic and inorganic MBBs. A MOF platform that has garnered particular attention, given its utility and fidelity in many different environments, is the fcu-MOF – a three-dimensional structure that is constructed from linking 12-coordinated face-centered cubic MBBs together. Since the discovery of the first Zr6 oxocluster-based fcu-MOF, known as UiO-66, there has been substantial progress in the synthesis of structures with varying metrics, but with the same underlying fcu topology. This family of fcu-MOFs has later evolved to incorporate isostructural, hexanuclear non-zirconium metal clusters, including rare earth, actinide and other transition metals as inorganic MBBs. Additionally, the versatility of the fcu-MOF platform for design has also attracted researchers to go beyond in situ generated hexanuclear metal clusters to transition metal-based non-hexanuclear metal oxocluster MBBs and metal–organic polyhedra (MOP) supermolecular building blocks (SBBs). All in all, reported fcu-MOFs are endowed with a wide range of porosity and framework chemistry, which has led to their applicability across energy and environmental sustainability issues of societal importance. In this review, a comprehensive assessment will be directed toward the synthesis and applications of fcu-MOFs with particular focus on the chemistry of the MBBs/SBBs and their resulting structure–property relationships. The synthetic and structural characterization challenges will be detailed with future opportunities becoming clear in the process.