Uranyl-Peroxide Capsule Self-Assembly in Slow Motion

被引：18

作者：

Arteaga, Ana ^{[1
]}

Zhang, Lei ^{[2
]}

Hickam, Sarah ^{[2
]}

Dembowski, Mateusz ^{[2
,3
]}

Burns, Peter C. ^{[2
]}

Nyman, May ^{[1
]}

机构：

[1] Oregon State Univ, Dept Chem, Corvallis, OR 97330 USA

[2] Univ Notre Dame, Dept Civil & Environm Engn & Earth Sci, Notre Dame, IN 46556 USA

[3] Pacific Northwest Natl Lab, Richland, WA 99352 USA

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2019年 / 25卷 / 24期

关键词：

calorimetry; crystal structure; polyoxometalates; uranyl; X-ray scattering; TRANSITION-METAL; CLUSTERS; DYNAMICS; STUDTITE; OXIDE;

D O I：

10.1002/chem.201806227

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Uranyl-peroxide capsules are the newest family of polyoxometalates. Although discovered 13 years previously with over 70 topologies reported, there is a lack in the fundamental understanding of assembly mechanisms, particularly the role of the alkali counterions. Herein, the reaction pathway and assembly of uranyl peroxide capsules is reported by tracking the conversion from K+ uranyl triperoxide monomer to the K+ uranyl-peroxide U-28 capsule by means of small-angle X-ray scattering and Raman spectroscopy. For the first time, the K+ uranyl-peroxide pentamer face is isolated and structurally characterized, giving credence to the long-held belief that these geometric faces serve as building blocks to the fully formed capsules. Once isolated and re-dissolved, the pentamer face undergoes rapid conversion to capsule forms, underlining its high reactivity that challenges its isolation. Calorimetric measurements of the studied species confirms the pentamer lies on the energy landscape between the monomer and capsule.

引用

页码：6087 / 6091

页数：5

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