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. 2020 Apr 16;26(22):5093-5099.
doi: 10.1002/chem.202000525. Epub 2020 Mar 31.

Template-Free Self-Assembly of Molecular Trefoil Knots and Double Trefoil Knots Featuring Cp*Rh Building Blocks

Wei-Long Shan  1   2 , Xiang Gao  1 , Yue-Jian Lin  1 , Guo-Xin Jin  1
Affiliations

Template-Free Self-Assembly of Molecular Trefoil Knots and Double Trefoil Knots Featuring Cp*Rh Building Blocks

Wei-Long Shan et al. Chemistry. .

Abstract

Understanding and controlling the topology of self-assembled structures plays a fundamental role in supramolecular chemistry. Herein, the preparation of a series of tetranuclear metallarectangles and hexanuclear trefoil knots featuring Cp*Rh building blocks by template-free self-assembly with four different rigid and flexible ligands is described. Transformations between the trefoil knots and the corresponding macrocycles can be induced by using concentration effects. Remarkably, the hexanuclear trefoil knot 5 was shown to assemble further to provide rare examples of [12+1] heteronuclear double trefoil knots (5 a/5 b/5 c/5 d) through coordination of the amide oxygen atoms to the secondary metal ions Na+ /K+ /Ca2+ /Cd2+ . The synthetic results are supported by single-crystal XRD.

Keywords: macrocycles; molecular knots; rhodium; self-assembly; supramolecular chemistry.

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