Publication

Article Metrics

Citations


Online attention

Lanthanide Template Synthesis of Trefoil Knots of Single Handedness

DOI: 10.1021/jacs.5b07069 DOI Help

Authors: Gen Zhang (School of Chemistry, University of Manchester, Oxford Road, Manchester) , Guzmán Gil-ramírez (School of Chemistry, University of Manchester, Oxford Road, Manchester) , Augustinas Markevicius (School of Chemistry, University of Manchester, Oxford Road, Manchester) , Colm Browne (School of Chemistry, University of Manchester, Oxford Road, Manchester) , Iñigo J. Vitorica-yrezabal (School of Chemistry, University of Manchester, Oxford Road, Manchester) , David Leigh (School of Chemistry, University of Manchester, Oxford Road, Manchester)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society , VOL 137 (32) , PAGES 10437 - 10442

State: Published (Approved)
Published: August 2015
Diamond Proposal Number(s): 8977

Open Access Open Access

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.

Subject Areas: Chemistry


Instruments: I19-Small Molecule Single Crystal Diffraction