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Towards the Development and Coordination Chemistry of Rotaxane- and Catenane-based Ligands

Towards the Development and Coordination Chemistry of Rotaxane- and Catenane-based Ligands
Towards the Development and Coordination Chemistry of Rotaxane- and Catenane-based Ligands
Rotaxanes and Catenanes are among the most studied platforms of mechanically interlocked molecules. The synthesis of these molecules has become easier with the development of the active template Cu-mediated alkyne-azide cycloaddition (AT-CuAAC) approach which allows the efficient synthesis of smaller rotaxanes and catenanes from accessible and versatile starting materials. The potential applications of these classes of molecules have been demonstrated in catalysis, sensing and the synthesis of mechanically chiral molecules. In this thesis, 2 aspects of the synthesis and application of rotaxanes and catenanes are addressed. Firstly, although bipyridine macrocycles are useful in the synthesis of small rotaxanes and catenanes, we set out to study if this efficient method could also be extended to mono-pyridine macrocycles. The other aspect is about their coordination chemistry. Despite the AT-CuAAC approach naturally producing interlocked ligands, the study of their coordination chemistry is relatively limited. Given that interlocked architectures have previously been reported to offer a binding pocket that leads to highly kinetically stablised complexes, we set out to design ligands to create complexes with high stability, ultimately for applications in medical imaging. In this thesis, the first chapter will introduce previously reported approaches to rotaxanes and catenanes from the statistical approach to the AT-CuAAC reaction, which will be employed in this work. The application in sensing, catalysis and chirality of rotaxanes and catenanes which were synthesized using the AT-CuAAC reaction is reviewed. The development of rotaxane- and catenane-based ligands for various types of transition metals is then discussed. In chapter 2, the development of rotaxane- and catenane-based ligands to towards highly kinetically stable CuII complexes is discussed. The third chapter focusses on the potential of pyridine functionalized macrocycles as an alternative to the bipyridine macrocycle for the synthesis of small rotaxane. The effect of binding site modification is also evaluated. Lastly, the possibility of using the catenane based ligand to tackle 2 fundamental issues for lanthanide coordination is testified.
University of Southampton
Boonprab, Theerapoom
32029d73-2beb-4a87-a299-878b85270f18
Boonprab, Theerapoom
32029d73-2beb-4a87-a299-878b85270f18
Goldup, Stephen
0a93eedd-98bb-42c1-a963-e2815665e937

Boonprab, Theerapoom (2022) Towards the Development and Coordination Chemistry of Rotaxane- and Catenane-based Ligands. University of Southampton, Doctoral Thesis, 537pp.

Record type: Thesis (Doctoral)

Abstract

Rotaxanes and Catenanes are among the most studied platforms of mechanically interlocked molecules. The synthesis of these molecules has become easier with the development of the active template Cu-mediated alkyne-azide cycloaddition (AT-CuAAC) approach which allows the efficient synthesis of smaller rotaxanes and catenanes from accessible and versatile starting materials. The potential applications of these classes of molecules have been demonstrated in catalysis, sensing and the synthesis of mechanically chiral molecules. In this thesis, 2 aspects of the synthesis and application of rotaxanes and catenanes are addressed. Firstly, although bipyridine macrocycles are useful in the synthesis of small rotaxanes and catenanes, we set out to study if this efficient method could also be extended to mono-pyridine macrocycles. The other aspect is about their coordination chemistry. Despite the AT-CuAAC approach naturally producing interlocked ligands, the study of their coordination chemistry is relatively limited. Given that interlocked architectures have previously been reported to offer a binding pocket that leads to highly kinetically stablised complexes, we set out to design ligands to create complexes with high stability, ultimately for applications in medical imaging. In this thesis, the first chapter will introduce previously reported approaches to rotaxanes and catenanes from the statistical approach to the AT-CuAAC reaction, which will be employed in this work. The application in sensing, catalysis and chirality of rotaxanes and catenanes which were synthesized using the AT-CuAAC reaction is reviewed. The development of rotaxane- and catenane-based ligands for various types of transition metals is then discussed. In chapter 2, the development of rotaxane- and catenane-based ligands to towards highly kinetically stable CuII complexes is discussed. The third chapter focusses on the potential of pyridine functionalized macrocycles as an alternative to the bipyridine macrocycle for the synthesis of small rotaxane. The effect of binding site modification is also evaluated. Lastly, the possibility of using the catenane based ligand to tackle 2 fundamental issues for lanthanide coordination is testified.

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More information

Submitted date: September 2021
Published date: January 2022

Identifiers

Local EPrints ID: 457021
URI: http://eprints.soton.ac.uk/id/eprint/457021
PURE UUID: 9d09a2f4-36d4-4b4e-81ba-116bc691f063
ORCID for Stephen Goldup: ORCID iD orcid.org/0000-0003-3781-0464

Catalogue record

Date deposited: 19 May 2022 16:47
Last modified: 16 Mar 2024 17:38

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Contributors

Author: Theerapoom Boonprab
Thesis advisor: Stephen Goldup ORCID iD

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