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Building [U IV 70 (OH) 36 (O) 64 ] 4− Oxocluster Frameworks with Sulfate, Transition Metals, and U V
Author(s) -
Colliard Ian,
Nyman May
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002403
Subject(s) - actinide , uranium , transition metal , sulfate , chemistry , crystallography , inorganic chemistry , oxide , crystal structure , oxidation state , thorium , metal , materials science , catalysis , metallurgy , biochemistry , organic chemistry
Uranium(IV) oxide clusters, colloids, and materials are designed and studied for 1) nuclear materials applications, 2) understanding the environmental fate and transport of actinides, and 3) exploring the complex bonding behavior of open‐shell f‐elements. U IV ‐oxyhydroxsulfate clusters are particularly relevant in industrial processes and in nature. Recent studies have shown that counter‐cations to these polynuclear anions differentiate rich structural topologies in the solid‐state. Herein, we present nine different structures with wheel‐shaped [U 70 (OH) 36 (O) 64 (SO 4 ) 60 ] 4− (U 70 ) linked into one‐ and two‐dimensional frameworks with sulfate, divalent transition metals (Cr II , Fe II , Co II , Ni II ) and U V . Small‐angle X‐ray scattering of these phases dissolved in butylamine reveals differing supramolecular assembly of U 70 clusters, controlled primarily by sulfates. However, observed trends in transition metal linking guide future design of U 70 materials with different topologies. Finally, U 70 linking via U IV ‐ O ‐U V ‐ O ‐U IV bridges presents a rare example of mixed‐oxidation‐state uranium oxides without disorder.