Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 20, Pages 5783-5787Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201802173
Keywords
coordination geometry; metal-organic frameworks; noble gases; open metal sites; thorium
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Funding
- National Science Foundation of China [21790370, 21790374, 21601131, 21761132019]
- Science Challenge Project [TZ2016004]
- Science Foundation of Jiangsu Province [BK20160312, 16KJB150035, 1501156B]
- General Financial Grant from the China Postdoctoral Science Foundation [2016M590493]
- Young Thousand Talented Program, a Project - Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
- State Key Laboratory of Photocatalysis on Energy and Environment [SKLPEE-KF201704]
- State Key Laboratory of Structural Chemistry [20170038]
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Actinide based metal-organic frameworks (MOFs) are unique not only because compared to the transition-metal and lanthanide systems they are substantially less explored, but also owing to the uniqueness of actinide ions in bonding and coordination. Now a 3D thorium-organic framework (SCU-11) contains a series of cages with an effective size of ca. 21 x 24 angstrom. Th4+ in SCU-11 is 10-coordinate with a bicapped square prism coordination geometry, which has never been documented for any metal cation complexes. The bicapped position is occupied by two coordinated water molecules that can be removed to afford a very unique open Th4+ site, confirmed by X-ray diffraction, color change, thermogravimetry, and spectroscopy. The degassed phase (SCU-11-A) exhibits a Brunauer-Emmett-Teller surface area of 1272 m(2) g(-1), one of the highest values among reported actinide materials, enabling it to sufficiently retain water vapor, Kr, and Xe with uptake capacities of 234 cm(3) g(-1), 0.77mmolg(-1), 3.17 mmol g(-1), respectively, and a Xe/Kr selectivity of 5.7.
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