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  • Review Article
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The active template approach to interlocked molecules

Nature Reviews Chemistry volume 1, Article number: 0061 (2017) Cite this article

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Abstract

The active template approach to interlocked molecules takes advantage of the ability of metal ions to both organize precursor fragments for mechanical bond formation and to mediate the final covalent bond-forming reaction that captures the interlocked structure. Since its inception just a decade ago, this new methodology has expanded rapidly from a single reaction for rotaxane synthesis to a range of metal-mediated bond formations for the synthesis of complex interlocked molecules. In this Review, we introduce the active template concept, its key advantages for the synthesis of interlocked molecules and outline recent advances that have been made using this technology. We will conclude with comments about future directions and challenges.

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Figure 1: Passive and active template synthesis of rotaxanes.
Figure 2: The formation of [3]rotaxanes in the AT-CuAAC reaction.
Figure 3: Complex interlocked molecules synthesized using the active template approach.
Figure 4: Interlocked electronic and oligomeric materials can be synthesized using the active template approach.
Figure 5: Interlocked molecules as catalysts.
Figure 6: Interlocked host molecules synthesized using the active template approach.
Figure 7: Examples of molecular machines synthesized using active template reactions.

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Acknowledgements

M.D. thanks the University of Southampton for financial support. S.M.G. acknowledges funding from the European Research Council (Consolidator Grant Agreement No. 724987) and is a Royal Society Research Fellow.

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  1. Department of Chemistry, University of Southampton, University Road, Southampton, SO17 1BJ, UK

    Mathieu Denis & Stephen M. Goldup

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  1. Mathieu Denis
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Correspondence to Stephen M. Goldup.

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PowerPoint slides

Glossary

Catenanes

Molecules composed of macrocycles that are threaded through one another like links in a chain.

Rotaxanes

Molecules in which macrocycles are threaded on linear axle components and locked in place by bulky ‘stopper’ units.

Mechanical bond

Two or more independent covalent species are said to be mechanically bonded when they are threaded through one another in such a way that they cannot be separated without breaking a covalent bond. The archetypal examples of mechanically bonded structures are catenanes and rotaxanes.

Stoppering

The process in which ‘stopper’ units are introduced at the ends of a threaded complex to trap the threaded architecture and form the mechanical bond.

Clipping

Cyclization of a pre-macrocycle (sometimes termed a U-shape) around a pre-formed axle to make a rotaxane, or starting from a threaded complex to form a catenane.

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Denis, M., Goldup, S. The active template approach to interlocked molecules. Nat Rev Chem 1, 0061 (2017). https://doi.org/10.1038/s41570-017-0061

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