Halogen bonding interlocked rotaxanes and transition metal-based host systems for charged guest recognition and sensing

<p>The main theme of this thesis is to incorporate multiple convergent halogen bonding (XB) donor motifs into anion binding sites of mechanically interlocked rotaxanes and transition metal-based host architectures and investigate their anion and ion-pair recognition capabilities.</p> &l...

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Detaylı Bibliyografya
Yazar: Munasinghe, AVK
Diğer Yazarlar: Beer, P
Materyal Türü: Tez
Dil:English
Baskı/Yayın Bilgisi: 2022
Konular:
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author Munasinghe, AVK
author2 Beer, P
author_facet Beer, P
Munasinghe, AVK
author_sort Munasinghe, AVK
collection OXFORD
description <p>The main theme of this thesis is to incorporate multiple convergent halogen bonding (XB) donor motifs into anion binding sites of mechanically interlocked rotaxanes and transition metal-based host architectures and investigate their anion and ion-pair recognition capabilities.</p> <p>Chapter 1 introduces the field of supramolecular host-guest chemistry with particular emphasis on XB interactions, anion and ion-pair recognition, followed by a review of the synthesis and applications of mechanically interlocked molecules (MIMs).</p> <p>Chapter 2 presents the first examples of a series of novel XB heteroditopic [2]rotaxanes capable of selectively recognising lithium halide ion-pair species. A co-bound lithium cation was observed to switch-on halide anion binding, and the binding affinity increased with the number of halogen bond donors. This initial work is extended to develop a dynamic two-station [2]rotaxane to investigate the unprecedented use of an ion-pair as an external stimulus to control the translational motion of the macrocycle along the axle component.</p> <p>Chapter 3 details the preparation, dicarboxylate anion recognition, and sensing properties of a novel iridium(III) complexed XB [3]rotaxane. The higher order mechanically bonded [3]rotaxane architecture exhibited higher luminescence quantum yields and superior anion recognition and sensing properties compared to analogous [2]rotaxane and acyclic hosts.</p> <p>Chapter 4 explores the design, synthesis, and anion binding properties of bimetallic rhenium(I) complexed molecular tweezer host systems containing a tetradentate XB binding cavity. Comprehensive anion binding studies revealed the significant contribution of both Re(I) complexation and tweezer design to the enhanced anion recognition properties observed by the tweezer hosts.</p> <p>Chapter 5 summarises the main conclusions of the thesis.</p> <p>Chapter 6 details the experimental procedures employed in this work, including synthetic protocols and the characterisation of novel compounds.</p>
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spelling oxford-uuid:5c5c20e3-1333-4d19-8971-fba22fe3d1d12024-09-09T13:56:26ZHalogen bonding interlocked rotaxanes and transition metal-based host systems for charged guest recognition and sensingThesishttp://purl.org/coar/resource_type/c_db06uuid:5c5c20e3-1333-4d19-8971-fba22fe3d1d1Supramolecular chemistryEnglishHyrax Deposit2022Munasinghe, AVKBeer, P<p>The main theme of this thesis is to incorporate multiple convergent halogen bonding (XB) donor motifs into anion binding sites of mechanically interlocked rotaxanes and transition metal-based host architectures and investigate their anion and ion-pair recognition capabilities.</p> <p>Chapter 1 introduces the field of supramolecular host-guest chemistry with particular emphasis on XB interactions, anion and ion-pair recognition, followed by a review of the synthesis and applications of mechanically interlocked molecules (MIMs).</p> <p>Chapter 2 presents the first examples of a series of novel XB heteroditopic [2]rotaxanes capable of selectively recognising lithium halide ion-pair species. A co-bound lithium cation was observed to switch-on halide anion binding, and the binding affinity increased with the number of halogen bond donors. This initial work is extended to develop a dynamic two-station [2]rotaxane to investigate the unprecedented use of an ion-pair as an external stimulus to control the translational motion of the macrocycle along the axle component.</p> <p>Chapter 3 details the preparation, dicarboxylate anion recognition, and sensing properties of a novel iridium(III) complexed XB [3]rotaxane. The higher order mechanically bonded [3]rotaxane architecture exhibited higher luminescence quantum yields and superior anion recognition and sensing properties compared to analogous [2]rotaxane and acyclic hosts.</p> <p>Chapter 4 explores the design, synthesis, and anion binding properties of bimetallic rhenium(I) complexed molecular tweezer host systems containing a tetradentate XB binding cavity. Comprehensive anion binding studies revealed the significant contribution of both Re(I) complexation and tweezer design to the enhanced anion recognition properties observed by the tweezer hosts.</p> <p>Chapter 5 summarises the main conclusions of the thesis.</p> <p>Chapter 6 details the experimental procedures employed in this work, including synthetic protocols and the characterisation of novel compounds.</p>
spellingShingle Supramolecular chemistry
Munasinghe, AVK
Halogen bonding interlocked rotaxanes and transition metal-based host systems for charged guest recognition and sensing
title Halogen bonding interlocked rotaxanes and transition metal-based host systems for charged guest recognition and sensing
title_full Halogen bonding interlocked rotaxanes and transition metal-based host systems for charged guest recognition and sensing
title_fullStr Halogen bonding interlocked rotaxanes and transition metal-based host systems for charged guest recognition and sensing
title_full_unstemmed Halogen bonding interlocked rotaxanes and transition metal-based host systems for charged guest recognition and sensing
title_short Halogen bonding interlocked rotaxanes and transition metal-based host systems for charged guest recognition and sensing
title_sort halogen bonding interlocked rotaxanes and transition metal based host systems for charged guest recognition and sensing
topic Supramolecular chemistry
work_keys_str_mv AT munasingheavk halogenbondinginterlockedrotaxanesandtransitionmetalbasedhostsystemsforchargedguestrecognitionandsensing