Emerging properties from mechanical tethering within a post-synthetically functionalised catenane scaffold

Maintaining close spatial proximity of functional moieties within molecular systems can result in fascinating emergent properties. Whilst much work has been done on covalent tethering of functional units for myriad applications, investigations into mechanically linked systems are relatively rare. Fo...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2022-10, Vol.13 (38), p.11368-11375
Main Authors: Hoyas Pérez, Nadia, Sherin, Peter S, Posligua, Victor, Greenfield, Jake L, Fuchter, Matthew J, Jelfs, Kim E, Kuimova, Marina K, Lewis, James E. M
Format: Article
Language:English
Subjects:
Chemical synthesis
Chemistry
Scaffolds
Tethering
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Summary:Maintaining close spatial proximity of functional moieties within molecular systems can result in fascinating emergent properties. Whilst much work has been done on covalent tethering of functional units for myriad applications, investigations into mechanically linked systems are relatively rare. Formation of the mechanical bond is usually the final step in the synthesis of interlocked molecules, placing limits on the throughput of functionalised architectures. Herein we present the synthesis of a bis-azide [2]catenane scaffold that can be post-synthetically modified using CuAAC 'click' chemistry. In this manner we have been able to access functionalised catenanes from a common precursor and study the properties of electrochemically active, emissive and photodimerisable units within the mechanically interlocked system in comparison to non-interlocked analogues. Our data demonstrates that the greater (co-)conformational flexibility that can be obtained with mechanically interlocked systems compared to traditional covalent tethers paves the way for developing new functional molecules with exciting properties. Using a post-synthetic modification strategy we have prepared a series of functionalised [2]catenanes to study the impact of mechanically-enforced proximity on functional group properties, including emission, electrochemistry and photoreactivity.
ISSN:2041-6520
2041-6539
DOI:10.1039/d2sc04101d