A complex core-shell cluster consisting of 68 uranyl peroxo polyhedra, 16 nitrate groups, and ~44 K(+) and Na(+) cations was obtained by self-assembly in alkaline aqueous solution under ambient conditions. Crystals formed after a month and were characterized. The cluster, designated as {U(1)⊂U(28)⊂U(40R)}, contains a fullerene-topology cage built from 28 uranyl polyhedra. A ring consisting of 40 uranyl polyhedra linked into five-membered rings and 16 nitrate groups surrounds this cage cluster. Topological pentagons in the cage and ring are aligned, and their corresponding rings of uranyl bipyramids are linked through K(+) cations located between the two shells. A partially occupied U site is located at the center of the cluster. Time-resolved small-angle X-ray scattering and electrospray ionization mass spectrometry demonstrated that the U(28) cage cluster formed in solution within an hour, whereas the U(40R) shell formed around the cage cluster after more than several days.
© 2011 American Chemical Society