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Active-template synthesis of small functionalised rotaxanes for sensing applications

Active-template synthesis of small functionalised rotaxanes for sensing applications
Active-template synthesis of small functionalised rotaxanes for sensing applications
Interlocked molecules, the archetypal examples of which are catenanes, and rotaxanes, have progressed over the last half-century from a significant synthetic challenge to readily accessible chemical species. The interest for these supramolecular architectures, which started from a purely aesthetic point of view, has further developed due to the high degree of freedom between its individual components. Controlling this motion via chemical or physical stimuli has resulted in the development of many stimuli-responsive interlocked systems with applications in wide range of field such as switches, molecular machinery and sensing. The latter is of particular interest as the mechanical bond within a catenane or rotaxane molecule creates a well-defined three-dimensional environment that can be readily functionalised to accommodate a variety of guest molecules. This thesis presents an investigation into the design and synthesis of novel functional rotaxane receptors and their application in the sensing of metal ions, anions and small chiral molecules.

The introductory chapter presents the active template approach to interlocked molecules. It highlights its key advantages and outline recent advances that have been made using this methodology. The following three chapters focus on the study of rotaxane receptors synthesised using this approach. Chapter two reports the synthesis of a sulfur-functionalised rotaxane and the investigation of its selective response for Zn2+ ion over other transition metal cations. Chapter three on the other hand focuses on a urea-based rotaxane that binds ion-pairs. This section will introduce preliminary results obtained with a simple model rotaxane before presenting its evolution into a stimuli-responsive receptor. The binding behaviour of both the rotaxane and related non-interlocked axle will be investigated to demonstrate the impact of the mechanical bond on the properties of the receptor. In the fourth chapter, the project was expanded toward chirality and more specifically enantioselective sensing. The development of a novel synthetic route to access functionalised mechanically planar chiral rotaxanes will be presented and it will conclude on preliminary binding studies of simple chiral anionic guest that shows enantioselectivity.
University of Southampton
Denis, Mathieu
05f9a9b4-df98-4cc8-bebf-33e99bc91e7d
Denis, Mathieu
05f9a9b4-df98-4cc8-bebf-33e99bc91e7d
Goldup, Stephen
0a93eedd-98bb-42c1-a963-e2815665e937

Denis, Mathieu (2017) Active-template synthesis of small functionalised rotaxanes for sensing applications. University of Southampton, Doctoral Thesis, 249pp.

Record type: Thesis (Doctoral)

Abstract

Interlocked molecules, the archetypal examples of which are catenanes, and rotaxanes, have progressed over the last half-century from a significant synthetic challenge to readily accessible chemical species. The interest for these supramolecular architectures, which started from a purely aesthetic point of view, has further developed due to the high degree of freedom between its individual components. Controlling this motion via chemical or physical stimuli has resulted in the development of many stimuli-responsive interlocked systems with applications in wide range of field such as switches, molecular machinery and sensing. The latter is of particular interest as the mechanical bond within a catenane or rotaxane molecule creates a well-defined three-dimensional environment that can be readily functionalised to accommodate a variety of guest molecules. This thesis presents an investigation into the design and synthesis of novel functional rotaxane receptors and their application in the sensing of metal ions, anions and small chiral molecules.

The introductory chapter presents the active template approach to interlocked molecules. It highlights its key advantages and outline recent advances that have been made using this methodology. The following three chapters focus on the study of rotaxane receptors synthesised using this approach. Chapter two reports the synthesis of a sulfur-functionalised rotaxane and the investigation of its selective response for Zn2+ ion over other transition metal cations. Chapter three on the other hand focuses on a urea-based rotaxane that binds ion-pairs. This section will introduce preliminary results obtained with a simple model rotaxane before presenting its evolution into a stimuli-responsive receptor. The binding behaviour of both the rotaxane and related non-interlocked axle will be investigated to demonstrate the impact of the mechanical bond on the properties of the receptor. In the fourth chapter, the project was expanded toward chirality and more specifically enantioselective sensing. The development of a novel synthetic route to access functionalised mechanically planar chiral rotaxanes will be presented and it will conclude on preliminary binding studies of simple chiral anionic guest that shows enantioselectivity.

Text
FINAL THESIS. Mathieu DENIS - Version of Record
Restricted to Repository staff only until 29 January 2021.
Available under License University of Southampton Thesis Licence.

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Published date: December 2017

Identifiers

Local EPrints ID: 418011
URI: http://eprints.soton.ac.uk/id/eprint/418011
PURE UUID: 797ea229-9cec-4103-bf5a-5193db6c82f4
ORCID for Stephen Goldup: ORCID iD orcid.org/0000-0003-3781-0464

Catalogue record

Date deposited: 20 Feb 2018 17:30
Last modified: 14 Mar 2019 01:33

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Contributors

Author: Mathieu Denis
Thesis advisor: Stephen Goldup ORCID iD

University divisions

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