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Bottom-up construction of a superstructure in a porous uranium-organic crystal

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Science  20 Apr 2017:
eaam7851
DOI: 10.1126/science.aam7851

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Abstract

Bottom-up construction of highly intricate structures from simple building blocks remains one of the most difficult challenges in chemistry. Here, we report a structurally complex, mesoporous uranium-based metal-organic framework (MOF) made from simple starting components. The structure is comprised of 10 uranium nodes and 7 tricarboxylate ligands (both crystallographically non-equivalent); resulting in a 173.3 angstrom cubic unit cell enclosing 816 uranium nodes and 816 organic linkers—the largest unit cell found for any nonbiological material. The cuboctahedra organize into pentagonal and hexagonal prismatic secondary structures which then form tetrahedral and diamond quaternary topologies with unprecedented complexity. This packing results in the formation of colossal icosidodecahedral and rectified hexakaidecahedral cavities with internal diameters of 5.0 nm and 6.2 nm, respectively—ultimately giving rise to the lowest density MOF reported to date.

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