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.

分子结构单元 (MBB) 的精确控制允许获得各种类型的定制功能材料。最好的例子是金属-有机框架 (MOF) 的组装，包括许多类型和排列的预先设计的有机和无机 MBB。鉴于其在许多不同环境中的实用性和保真度，一个受到特别关注的 MOF 平台是fcu -MOF——一种由 12 个配位面心立方 MBB 连接在一起构成的三维结构。自从发现第一个基于 Zr _6氧簇的fcu -MOF（称为 UiO-66）以来，在具有不同指标但具有相同基础fcu的结构的合成方面取得了实质性进展拓扑。这个fcu -MOFs 家族后来演变为包含等结构的六核非锆金属簇，包括稀土、锕系元素和其他过渡金属作为无机 MBB。此外，用于设计的fcu -MOF 平台的多功能性也吸引了研究人员超越原位生成的六核金属簇，转向基于过渡金属的非六核金属氧簇 MBB 和金属有机多面体 (MOP) 超分子构件 (SBB) . 总而言之，报告了fcu-MOFs 具有广泛的孔隙率和骨架化学特性，这使其适用于具有社会重要性的能源和环境可持续性问题。在这篇综述中，将针对fcu -MOFs 的合成和应用进行全面评估，特别关注 MBBs/SBBs 的化学性质及其产生的结构-性质关系。合成和结构表征挑战将详细说明，未来机会在此过程中变得清晰。