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

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• 作者：Jie Qiu ; Mateusz Dembowski ; Jennifer E. S. Szymanowski ; Wen Cong Toh ; Peter C. Burns
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：July 18, 2016
• 年：2016
• 卷：55
• 期：14
• 页码：7061-7067
• 全文大小：521K
• 年卷期：0
• ISSN：1520-510X

文摘

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.