5 years ago

Supramolecular Isomers of Coordination-Directed Side-Chain Polypseudorotaxanes Based on Trimeric Uranyl Oxalate Nodes

Supramolecular Isomers of Coordination-Directed Side-Chain Polypseudorotaxanes Based on Trimeric Uranyl Oxalate Nodes
Zhi-fang Chai, Wei-qun Shi, Lei Mei, Kong-qiu Hu, Xiao-lin Wang, Yun-chen Ge, Chuan-qin Xia, Zhen-ni Xie
Although the prosperity of rotaxane coordination polymers with rotaxane molecules serving as main-chain linkers is known, side-chain metal-organic polypseudorotaxanes incorporating macrocyclic host molecules have not been reported to date. Herein a new type of coordination-driven cucurbit[6]uril-bearing side-chain polypseudorotaxane, with two-dimensional trimeric uranyl-oxalate as main chains, has been synthesized. This was carried out through hydrothermal reactions of uranyl components with an in situ-formed carboxylated pseudorotaxane ligand in the presence of oxalate co-ligands. Varying the substitution site of coordination groups led to two different supramolecular isomers. Further mechanistic analysis indicated that condition-dependent hydrolysis of the cyano groups of the pseudorotaxane ligand, as well as the participation of oxalate groups into the coordination sphere of uranyl moieties, contributes to the formation of this new type of side-chain polypseudorotaxane. Blocks of U: A coordination-driven cucurbit[6]uril-bearing side-chain polypseudorotaxane with two-dimensional trimeric uranyl-oxalate main chains has been synthesized through hydrothermal reaction of uranyl components with a unique semi-hydrolytic pseudorotaxane linker formed in the presence of oxalate co-ligands.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701706

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