Selective Construction of Trefoil knots and a Molecular Borromean Ring Induced by Steric Hindrance of Thioether Ligands |
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Authors: | Hai-Ning Zhang Dr. Yue-Jian Lin Prof. Guo-Xin Jin |
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Affiliation: | Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, State Key Laboratory of Molecular Engineering of Polymers, Department of Chemistry, Fudan University, Shanghai, 200433 P. R. China |
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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. |
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Keywords: | Borromean ring selective synthesis steric hindrance thioether ligands trefoil knot |
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