4.8 Article

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

期刊

SCIENCE
卷 356, 期 6338, 页码 624-627

出版社

AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.aam7851

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  1. U.S. Department of Energy (DOE) Office of Science, Basic Energy Sciences Program [DE-FG02-08ER155967]
  2. Natural Sciences a.nd Engineering Research Council of Canada
  3. Soft and Hybrid Nanotechnology Experimental Resource (NSF) [NNCI-1542205]
  4. State of Illinois
  5. International Institute for Nanotechnology
  6. Chemical Imagirig Initiative Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory (PNNL)
  7. DOE [DE-AC05-76RL01830]
  8. DOE Office of Biological and Environmental Research

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Bottom-up construction of highly intricate structures from simple building blocks remains one of the most difficult challenges in chemistry. We report a structurally complex, mesoporous uranium-based metal-organic framework (MOF) made from simple starting components. The structure comprises 10 uranium nodes and seven tricarboxylate ligands (both crystallographically nonequivalent), resulting in a 173.3-angstrom cubic unit cell enclosing 816 uranium nodes and 816 organic linkers-the largest unit cell found to date 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 nanometers and 6.2 nanometers, respectively-ultimately giving rise to the lowest-density MOF reported to date.

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