As compared to porous network solids, including metal–organic frameworks, covalent–organic frameworks, porous aromatic frameworks, and zeolites, porous molecular materials are relatively unexplored. Additionally, within porous molecular space, porous organic cages (POCs) have been the most widely reported over the past decade. Relatively recently, however, porous hybrid metal–organic molecular complexes have received considerable attention with a large fraction of surface areas for these coordination cages reported over the past three years. This review focuses on advances in this area. We highlight the recent work with permanently microporous metal–organic polyhedra (MOPs). Analogous to early work in the area of MOFs, the vast majority of MOPs for which surface areas have been reported have been based on paddlewheel building units and carboxylate ligands. We describe the synthesis of porous cages and highlight those based on monometallic, bimetallic, trimetallic, tetrametallic, and higher nuclearity clusters. Finally, we showcase work wherein the porosity of MOPs has been leveraged for applications related to the storage and separation of small molecules and the incorporation of these porous and potentially porous cages into membranes.

中文翻译：

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永久微孔金属有机多面体。

与包括金属-有机骨架，共价-有机骨架，多孔芳族骨架和沸石的多孔网络固体相比，多孔分子材料的开发还相对较少。另外，在多孔分子空间内，多孔有机笼（POC）在过去十年中得到了最广泛的报道。然而，相对较近的几年来，多孔配位金属-有机分子复合物受到了相当大的关注，在过去三年中，这些配位笼的表面积很大。这篇综述着重介绍了该领域的进展。我们重点介绍了永久微孔金属-有机多面体（MOP）的最新研究。与MOF领域的早期工作类似，据报道表面积的绝大多数MOP是基于桨轮构建单元和羧酸盐配体。我们描述了多孔笼的合成，并重点介绍了基于单金属，双金属，三金属，四金属和更高原子核簇的笼。最后，我们展示了MOP的孔隙度已被用于与小分子的存储和分离以及将这些多孔和潜在的多孔笼子并入膜相关的应用的工作。