An Unprecedented Two‐Fold Nested Super‐Polyrotaxane: Sulfate‐Directed Hierarchical Polythreading Assembly of Uranyl Polyrotaxane Moieties |
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Authors: | Dr. Lei Mei Dr. Qun‐yan Wu Dr. Li‐yong Yuan Dr. Lin Wang Shu‐wen An Zhen‐ni Xie Dr. Kong‐qiu Hu Prof. Zhi‐fang Chai Prof. Peter C. Burns Prof. Wei‐qun Shi |
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Affiliation: | 1. Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, P.R. China;2. School of Radiological and Interdisciplinary Sciences and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, Suzhou, P.R. China;3. Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN, USA |
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Abstract: | The hierarchical assembly of well‐organized submoieties could lead to more complicated superstructures with intriguing properties. We describe herein an unprecedented polyrotaxane polythreading framework containing a two‐fold nested super‐polyrotaxane substructure, which was synthesized through a uranyl‐directed hierarchical polythreading assembly of one‐dimensional polyrotaxane chains and two‐dimensional polyrotaxane networks. This special assembly mode actually affords a new way of supramolecular chemistry instead of covalently linked bulky stoppers to construct stable interlocked rotaxane moieties. An investigation of the synthesis condition shows that sulfate can assume a vital role in mediating the formation of different uranyl species, especially the unique trinuclear uranyl moiety [(UO2)3O(OH)2]2+, involving a notable bent [O=U=O] bond with a bond angle of 172.0(9)°. Detailed analysis of the coordination features, the thermal stability as well as a fluorescence, and electrochemical characterization demonstrate that the uniqueness of this super‐polyrotaxane structure is mainly closely related to the trinuclear uranyl moiety, which is confirmed by quantum chemical calculations. |
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Keywords: | actinides polythreading rotaxanes supramolecular chemistry uranium |
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