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1 PublicationMOFs with 12-coordinate 5f-block metal centers
Lv, K.; Urbank, C.; Patzschke, M.; März, J.; Kaden, P.; Weiß, S.; Schmidt, M.
Abstract
We have constructed an unprecedented MOF platform that accommodates a range of 5f-block metal ions (Th4+, U4+, Np4+, Pu4+) as the primary building block. The isoreticular actinide metal-organic frameworks (An-MOFs) exhibit periodic trends in the 12-coordinate metal environment, ligand configuration, and resulting ultramicroporosity. It holds potential in distinguishing neighboring tetravalent actinides. The metal ionic radius, carboxylate bite angle, anthracene plane twisting, inter-ligand interac-tions, and countercation templating collectively determine an interplay between solvation, modulation, and complexation, re-sulting in a coordination saturation of the central actinide while lanthanide counterparts are stabilized by the formation of a dimer-based motif. Quantum chemical calculations indicate that this large coordination number is only feasible in the high-symmetry environment provided by the An-MOFs. This category of MOFs not only demonstrates autoluminescence (4.16 ×104 counts per second per gram) but also portends a wide-bandgap (2.84 eV) semiconducting property with implications for a multitude of applications such as hard radiation detection.
Keywords: Actinides; Metal-Organic Frameworks; Autoluminescence; Semiconductor
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Data publication: MOFs with 12-coordinate 5f-block metal centers
ROBIS: 34272 HZDR-primary research data are used by this (Id 34224) publication
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Journal of the American Chemical Society 144(2022)7, 2879-2884
DOI: 10.1021/jacs.1c13127
Cited 14 times in Scopus
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