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. 2021 Jul 19;16(14):1918-1924.
doi: 10.1002/asia.202100450. Epub 2021 May 18.

Selective Construction of Trefoil knots and a Molecular Borromean Ring Induced by Steric Hindrance of Thioether Ligands

Hai-Ning Zhang  1 , Yue-Jian Lin  1 , Guo-Xin Jin  1
Affiliations

Selective Construction of Trefoil knots and a Molecular Borromean Ring Induced by Steric Hindrance of Thioether Ligands

Hai-Ning Zhang et al. Chem Asian J. .

Abstract

Two Cp*-RhIII based trefoil knots were obtained in high yield under ambient conditions via the coordination-driven self-assembly of semi-rigid thioether dipyridyl ligand 1,4-bis[(pyridin-4-ylthio)methyl]benzene (L1 ), ligand chloranilic acid (H2 -CA) and 6,11-dihydroxytetracene-5,12-dione (H2 -TtDo) with Cp*RhIII metal corner units, respectively. Furthermore, using the bulkier 4,4'-{[(2,5-dimethyl-1,4-phenylene)bis(methylene)]bis(sulfanediyl)}dipyridine (L2 ) in the place of ligand L1 in the construction process resulted in the formation of a teranuclear metallacycle and a template-free Borromean ring in high yields thanks to significantly altered intermolecular forces between the constituent ligands induced by the sterically-hindering methyl groups of L2 , as demonstrated via a detailed X-ray crystallographic analysis and NMR spectroscopy.

Keywords: Borromean ring; selective synthesis; steric hindrance; thioether ligands; trefoil knot.

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