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Controlling the shape and chirality of an eight-crossing molecular knot

Accepted version
Peer-reviewed

Type

Article

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Authors

Carpenter, JP 
Ronson, TK 

Abstract

The knotting of biomolecules impacts their function, and enables them to carry out new tasks. Likewise, complex topologies underpin the operation of many synthetic molecular machines. The ability to generate and control more complex knotted architectures is essential to endow these machines with more advanced functions. Here we report the synthesis of a molecular knot with eight crossing points, consisting of a single organic loop woven about six templating metal centres, <i>via</i> one-pot self-assembly from a simple pair of dialdehyde and diamine subcomponents and a single metal salt. The structure and topology of the knot were established by NMR spectroscopy, mass spectrometry and X-ray crystallography. Upon demetallation, the purely organic strand relaxes into a symmetric conformation, whilst retaining the topology of the original knot. This knot is topologically chiral, and may be synthesised diastereoselectively through the use of an enantiopure diamine building block.

Description

Keywords

3402 Inorganic Chemistry, 3403 Macromolecular and Materials Chemistry, 3405 Organic Chemistry, 34 Chemical Sciences

Journal Title

Chem

Conference Name

Journal ISSN

2451-9308
2451-9294

Volume Title

Publisher

Elsevier BV

Rights

All rights reserved
Sponsorship
Engineering and Physical Sciences Research Council (EP/P027067/1)
European Research Council (695009)
European Commission (264645)
This work was supported by the European Research Council (695009), the UK Engineering and Physical Sciences Research Council (EPSRC EP/P027067/1), networking contributions from the COST Action CA17139, EUTOPIA, and a Marie Curie fellowship for J.P.C. (ITN-2010-264645). C.T.M. thanks the Leverhulme and Isaac Newton Trusts, and Sidney Sussex College, Cambridge, for Fellowship support. The authors thank the Department of Chemistry NMR Facility, University of Cambridge for performing some NMR experiments, the EPSRC UK National Mass Spectrometry Facility at Swansea University and the Department of Chemistry Mass Spectrometry Facility, University of Cambridge, for carrying out high resolution mass spectrometry, and Diamond Light Source (UK) for synchrotron beamtime on I19 (MT15768)
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