Coordination-driven assembly of actinide-organic polyrotaxanes involving crown ether macrocycles

• Published in: Organic chemistry frontiers an international journal of organic chemistry Vol. 8; no. 14; pp. 3686 - 3694
• Main Authors: Jing-yang, Wang, Wu, Qun-yan, Wang, Shuai, Zhi-wei, Huang, Kong-qiu, Hu, Ji-pan, Yu, Lei Mei, Zhang, Meng, Zhi-fang Chai, Wei-qun Shi
• Format: Journal Article
• Language: English
• Published: London Royal Society of Chemistry 21.07.2021
• Subjects: Assembly; Coordination polymers; Crown ethers; Crystal structure; Crystallography; Ions; Molecular structure; Organic chemistry; Polymers; Rotaxanes
• ISSN: 2052-4110; 2052-4110
• DOI: 10.1039/d1qo00536g

Research on synthesizing new coordination-driven polyrotaxanes as well as regulating their structural diversity contributes to the success of macrocycle-based supramolecular materials. In this work, we describe the synthesis of a new kind of actinide-organic polyrotaxane involving crown ether macrocycles for the first time. Crystal structures of two uranyl polyrotaxane compounds, UCER-1 and UCER-2, as well as a third non-polyrotaxane compound UON-1, have been determined, and the formation mechanism of actinide-organic polyrotaxanes is discussed in terms of factors affecting the assembly process. A comparison of the reaction conditions and the corresponding outcomes suggests the necessity of a host–guest pseudorotaxane linker for the successful construction of targeted actinide-organic polyrotaxanes. The coordination of different coordination atoms, especially bromide ions and uranyl ions, is analyzed in detail through theoretical calculations. As an extension of cucurbituril-based uranyl-organic polyrotaxanes, the introduction of crown ether macrocycles as a new supramolecular element brings a different kind of actinide polyrotaxane with intriguing molecular structures and supramolecular assembly behaviours, and will, we believe, expand the research scope of actinide rotaxane coordination polymers.