Time-Resolved X-ray Scattering and Raman Spectroscopic Studies of Formation of a Uranium-Vanadium-Phosphorus-Peroxide Cage Cluster

摘要

Combining reactants in water under ambient conditions results in the assembly and crystallization of 2.6 nm diameter cage clusters designated U48V6P48 within 3 weeks. These consist of 24 uranyl hexagonal bipyramids, 24 uranyl pentagonal bipyramids, six vanadyl square pyramids, and 48 phosphate tetrahedra. Peroxide-bridged dimers of uranyl hexagonal bipyramids are linked directly to vanadyl-stabilized tetramers of uranyl pentagonal bipyramids to form the cage, with phosphate tetrahedra providing additional linkages between these two units. Time-resolved small-angle X-ray scattering and Raman spectroscopy indicate that the combination of the reactants initially resulted in simultaneous formation of smaller uranyl peroxide cages and vanadyl peroxide complexes. The disappearance of the smaller uranyl peroxide cages from solution coincides with the diminution of uncoordinated peroxide, both of which occurred before the assembly of the relatively peroxide-poor U48V6P48, which clearly occurred in solution prior to its crystallization.