Lanthanide template synthesis of trefoil knots of single handedness

Zhang, Gen and Gil-Ramírez, Guzmán and Markevicius, Augustinas and Browne, Colm and Vitorica-Yrezabal, Iñigo J. and Leigh, David A. (2015) Lanthanide template synthesis of trefoil knots of single handedness. Journal of the American Chemical Society, 137 (32). pp. 10437-10442. ISSN 0002-7863

Full content URL: http://dx.doi.org/10.1021/jacs.5b07069

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Item Type:Article
Item Status:Live Archive

Abstract

We report on the assembly of 2,6-pyridinedicarboxamide ligands (1) with point chirality about lanthanide metal ion (Ln3+) templates, in which the helical chirality of the resulting entwined 3:1 ligand:metal complexes is covalently captured by ring-closing olefin metathesis to form topologically chiral molecular trefoil knots of single handedness. The ligands do not self-sort (racemic ligands form a near-statistical mixture of homoleptic and heteroleptic lanthanide complexes), but the use of only (R,R)-1 leads solely to a trefoil knot of Λ-handedness, whereas (S,S)-1 forms the Δ-trefoil knot with complete stereoselectivity. The knots and their isomeric unknot macrocycles were characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography and the expression of the chirality that results from the topology of the knots studied by circular dichroism.

Keywords:Chiral, JCOpen
Subjects:F Physical Sciences > F100 Chemistry
Divisions:College of Science > School of Chemistry
ID Code:22710
Deposited On:18 Mar 2016 19:44

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