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A family of diastereomeric dodecanuclear coordination cages based on inversion of chirality of individual triangular cyclic helicate faces
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Argent, Stephen P., Jackson, Fiona C., Chan, Ho Man, Meyrick, Sam, Taylor, Christopher G. P., Ronson, Tanya K., Rourke, Jonathan P. and Ward, Michael D. (2020) A family of diastereomeric dodecanuclear coordination cages based on inversion of chirality of individual triangular cyclic helicate faces. Chemical Science, 11 (37). pp. 10167-10174. doi:10.1039/d0sc04347h ISSN 2041-6520.
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WRAP-family-diastereomeric-dodecanuclear-coordination-cages-based-inversion-chirality-individual-triangular-cyclic-helicate-faces-Ward-2020.pdf - Published Version - Requires a PDF viewer. Available under License Creative Commons Attribution. Download (1071Kb) | Preview |
Official URL: http://dx.doi.org/10.1039/d0sc04347h
Abstract
The dodecanuclear coordination cage [Cd12(Lnaph)12(Lmes)4](BF4)24 consists of a set of four triangular, trinuclear helical panels {Cd3(μ-Lnaph)3}6+ (based on ditopic bridging ligands Lnaph), which are connected by four tritopic ligands Lmes. The result is that the four triangular helical panels and the four Lmes-capped triangular faces of the cuboctahedral core form two alternating subsets of the eight triangular faces of the cuboctahedron. Crystallographic investigations revealed that the triangular helicate faces can have ‘clockwise’ (C) or ‘anticlockwise’ (A) helicity, and that the helicity of each face can vary independently of the others as they are mechanically separated. This generates a set of three diastereoisomers in which all four cyclic helicate faces in the cuboctahedron have the same chirality (AAAA/CCCC enantiomers with T symmetry; AAAC/CCCA enantiomers with C3 symmetry; and achiral AACC with S4 symmetry). This mirrors the known behaviour of many simpler M4L6 tetrahedral cages which can likewise exist as T, C3 or S4 isomers according to the sense of tris-chelate chirality around each individual metal centre: but here it is translated onto a much larger scale by the four chiral units being entire trinuclear helicate faces rather than single metal centres. 1H NMR spectroscopy confirms the presence of the three diastereoisomers with their different molecular symmetries in a ratio slightly different from what is expected on purely statistical grounds; and 1H NMR measurements on a non-equilibrium sample (enriched by manual crystal-picking before preparing the solution) showed that the distribution does not change over several weeks in solution, indicating the kinetic inertness of the cage assemblies.
| Item Type: | Journal Article | |||||||||
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| Subjects: | Q Science > QD Chemistry | |||||||||
| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | |||||||||
| Library of Congress Subject Headings (LCSH): | Mass spectrometry, X-ray crystallography , Ligands (Biochemistry) , Metal ions | |||||||||
| Journal or Publication Title: | Chemical Science | |||||||||
| Publisher: | Royal Society of Chemistry | |||||||||
| ISSN: | 2041-6520 | |||||||||
| Official Date: | 2020 | |||||||||
| Dates: |
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| Volume: | 11 | |||||||||
| Number: | 37 | |||||||||
| Page Range: | pp. 10167-10174 | |||||||||
| DOI: | 10.1039/d0sc04347h | |||||||||
| Status: | Peer Reviewed | |||||||||
| Publication Status: | Published | |||||||||
| Access rights to Published version: | Open Access (Creative Commons) | |||||||||
| Date of first compliant deposit: | 9 October 2020 | |||||||||
| Date of first compliant Open Access: | 13 October 2020 | |||||||||
| RIOXX Funder/Project Grant: |
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