Crown and bowl-shaped clusters of uranyl polyhedra.

Bowl (U(16)) and crown-shaped clusters (U(20R) and U(24R)) containing 16, 20, and 24 uranyl peroxide polyhedra self-assemble in alkaline aqueous solution under ambient conditions. Structural analyses of crystallized clusters provided details of their topologies. Each contains uranyl hexagonal bipyramids in which two cis edges are peroxide, with a third edge defined by two OH groups, as well as hexagonal bipyramids in which three edges are peroxide. These are the first open uranyl peroxide clusters reported, and they join a growing family of complex cluster topologies based on uranium that hold promise for nanoscale control of chemistry in nuclear energy cycles.