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Interlocked molecules with unusual properties: luminescent rotaxanes and mechanically chiral catenanes

Interlocked molecules with unusual properties: luminescent rotaxanes and mechanically chiral catenanes
Interlocked molecules with unusual properties: luminescent rotaxanes and mechanically chiral catenanes
Once merely a synthetic curiosity, mechanically interlocked molecules (MIMs) have become readily accessible structures thanks to the development of template approaches, and their properties are now being explored for applications in materials, catalysis, sensing, and molecular machines. This thesis describes work to expand the understanding and applications of MIMs prepared via an active template approach. In the first chapter, topics related to MIMs are discussed with the aim of introducing the work presented in chapters 2-4. These include the active template copper-mediated azide alkyne cycloaddition, emissive rotaxanes, and the stereogenic units that can arise from the mechanical bond. In the second, the synthesis of a selection of rotaxanes based on a thermally activated delayed fluorescence (TADF) emitter scaffold is reported. The effect of the mechanical bond on the TADF properties of three of these emitters was investigated and was shown to improve key photophysical properties. In the third, the synthesis of cycloplatinated rotaxanes is explored for potential applications in luminescent materials. A robust procedure could not be developed. However, the platination exhibited unexpected regioselectivity depending on the components used to prepare the rotaxanes, highlighting the ability of the mechanical bond to influence unexplored reactivities. Finally, in the fourth chapter, the concept of topological chirality in MIMs is discussed. Using a chiral auxiliary approach developed by the Goldup group, a chiral catenane is synthesised where an exocyclic double bond determines the orientation of one ring, challenging common terminology used to describe such stereogenic units.
University of Southampton
Rizzi, Federica
f05be5f8-7711-4796-9cd3-9fa5b238ea3e
Rizzi, Federica
f05be5f8-7711-4796-9cd3-9fa5b238ea3e
Goldup, Stephen
0a93eedd-98bb-42c1-a963-e2815665e937

Rizzi, Federica (2022) Interlocked molecules with unusual properties: luminescent rotaxanes and mechanically chiral catenanes. University of Southampton, Doctoral Thesis, 336pp.

Record type: Thesis (Doctoral)

Abstract

Once merely a synthetic curiosity, mechanically interlocked molecules (MIMs) have become readily accessible structures thanks to the development of template approaches, and their properties are now being explored for applications in materials, catalysis, sensing, and molecular machines. This thesis describes work to expand the understanding and applications of MIMs prepared via an active template approach. In the first chapter, topics related to MIMs are discussed with the aim of introducing the work presented in chapters 2-4. These include the active template copper-mediated azide alkyne cycloaddition, emissive rotaxanes, and the stereogenic units that can arise from the mechanical bond. In the second, the synthesis of a selection of rotaxanes based on a thermally activated delayed fluorescence (TADF) emitter scaffold is reported. The effect of the mechanical bond on the TADF properties of three of these emitters was investigated and was shown to improve key photophysical properties. In the third, the synthesis of cycloplatinated rotaxanes is explored for potential applications in luminescent materials. A robust procedure could not be developed. However, the platination exhibited unexpected regioselectivity depending on the components used to prepare the rotaxanes, highlighting the ability of the mechanical bond to influence unexplored reactivities. Finally, in the fourth chapter, the concept of topological chirality in MIMs is discussed. Using a chiral auxiliary approach developed by the Goldup group, a chiral catenane is synthesised where an exocyclic double bond determines the orientation of one ring, challenging common terminology used to describe such stereogenic units.

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More information

Published date: March 2022

Identifiers

Local EPrints ID: 467870
URI: http://eprints.soton.ac.uk/id/eprint/467870
PURE UUID: 9a0e5201-dcf8-4b20-8573-2c74f5e188cd
ORCID for Stephen Goldup: ORCID iD orcid.org/0000-0003-3781-0464

Catalogue record

Date deposited: 22 Jul 2022 16:48
Last modified: 16 Mar 2024 21:20

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Contributors

Author: Federica Rizzi
Thesis advisor: Stephen Goldup ORCID iD

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