Uranyl peroxide nanoclusters have been intensively investigated due to their potential applications in the advanced nuclear energy system. Here we reported isolations and structures of the largest actinide cluster U124PO4 containing 124 uranyl peroxide polyhedra and 32 phosphate tetrahedral, and fragments of uranyl peroxides, including dimers, tetramers, pentamers and hexamers of uranium. Structural examinations of these fragments and previous published cage clusters revealed that the flexibility of 'side-on' bridge U-O2-U favored formations of different building blocks of clusters, which can provide different curvatures for clusters, and incorporations of additional 'side-on' bridges such as U-(OH)2-U, U-C2O4-U, and U-P2O7-U also can tune sizes and topologies of clusters, however, size increases of clusters are limited using these ways. For giant U124PO4, bridges between uranyl polyhedra by sharing vertices and/or edges with phosphate tetrahedra are very important for its formation, indicating that replacements of non-peroxide 'side-on' bridges are effective way to grow larger clusters with new topologies.Figure 1.  Ball-stick (a) and polyhedral (b) representations of U124PO4 along the -4 rotational axis. Note that U124PO4 can be considered to be built from the central cage cluster U52PO4 (c) and four surrounding open clusters U18 (d). Uranium atoms and polyhedra are in yellow, and O atoms in red. Tetrahedron of H2PO4-, HPO42-, and PO43-groups and corresponding P atoms are in purple, green, and black, respectively.

How to control sizes of uranyl-peroxide cage nanoclusters

246th National Meeting (2013)

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