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Supramolecular Host–Guest Inclusion for Distinguishing Cucurbit[7]uril‐Based Pseudorotaxanes from Small‐Molecule Ligands in Coordination Assembly with a Uranyl Center
Author(s) -
Mei Lei,
Xie ZhenNi,
Hu Kongqiu,
Yuan LiYong,
Gao ZengQiang,
Chai ZhiFang,
Shi WeiQun
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201702752
Subject(s) - supramolecular chemistry , chemistry , uranyl , cucurbituril , ligand (biochemistry) , rotaxane , molecule , crystallography , linker , stereochemistry , supramolecular assembly , coordination complex , metal , organic chemistry , receptor , ion , biochemistry , computer science , operating system
Abstract Although the capability of supramolecular pseudorotaxane/rotaxane systems as ligands for coordination with actinides has been identified by the on‐going emerging of uranyl–organic polyrotaxane compounds, it is, however, still unknown how supramolecular inclusion affects the coordination assembly of the simple “axle” ligand with uranyl species. Herein, a semi‐rigid organic dicarboxylate compound [BzBPCEt]Br 2 ( L 1 ) is selected as a small‐molecule “axle” ligand and the corresponding cucurbit[7]uril ( CB7 )‐based [2]pseudorotaxane ligand, [BzBPCEt]Br 2 @ CB7 ( L 1 @ CB7 ) has been also synthesized through CB7 ‐based inclusion in this work. A detailed comparison between uranyl complexes from the “axle” ligand L 1 and those from pseudorotaxane L 1 @ CB7 has been conducted, demonstrating the significant role of CB7 ‐based inclusion in distinguishing supramolecular pseudorotaxane ligands from small‐molecule dicarboxylates in uranyl coordination assembly. Notably, the impact of supramolecular inclusion on the “axle” linker in the system with cucurbituril macrocycles involved is established for the first time. Detailed structure decipherment suggests that the significant effect of CB7 is attributed to hydrothermal stabilization of the “axle” ligand or increased steric hindrance to the groups nearby originated from the bulky size of macrocyclic CB7 .