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