Halogen bonding interlocked host systems for recognition and sensing of charged guests
<p>This thesis describes the development of cation and anion template-directed methodologies to prepare interlocked host molecules for the recognition of charged guests, principally anions and ion-pairs. The use of halogen bonding motifs as both anion templating and binding motifs is explored...
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| Format: | Thesis |
| Language: | English |
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2024
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| _version_ | 1826314470618562560 |
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| author | Tay, HM |
| author2 | Beer, P |
| author_facet | Beer, P Tay, HM |
| author_sort | Tay, HM |
| collection | OXFORD |
| description | <p>This thesis describes the development of cation and anion template-directed methodologies to prepare interlocked host molecules for the recognition of charged guests, principally anions and ion-pairs. The use of halogen bonding motifs as both anion templating and binding motifs is explored as a strategy to enhance the ion recognition properties of the interlocked hosts.</p>
<p><strong>Chapter 1</strong> introduces the field of supramolecular chemistry and outlines the key principles underlying host-guest chemistry. Advances in the design of receptors for anion and ion-pair recognition are reviewed, with a particular focus on receptors utilising halogen bonding (XB) interactions. The template-directed preparation of mechanically interlocked molecules and their applications in host-guest recognition and sensing is discussed.</p>
<p><strong>Chapter 2</strong> describes the ion-pair binding properties of neutral heteroditopic XB catenanes and rotaxanes prepared via an alkali metal cation template-directed approach. The binding of alkali metal cations, halide anions and their respective ion-pairs by the interlocked hosts is investigated by 1H NMR titration studies, revealing significant positive cooperativity between cation and anion binding events. Crystallographic analysis is used to probe the binding modes and stoichiometries of the catenane receptors. The ion-pair binding capabilities of the receptors are also exploited for the selective solid-liquid extraction of alkali metal halide salts.</p>
<p><strong>Chapter 3</strong> describes the use of a novel chloride anion template-directed strategy to prepare neutral XB [2]catenane and [2]rotaxane interlocked host molecules. 1H NMR binding studies of the host molecules in aqueous-acetone solvent mixtures demonstrate a mechanical bond induced anti-Hofmeister halide anion binding preference, which is exploited to develop selective interlocked systems for anion membrane transport and sensing.</p>
<p><strong>Chapter 4</strong> details the use of orthogonal cation and anion template-directed strategies to prepare a heteroditopic [3]catenane possessing interlocked binding cavities for both the cationic and anionic guests. Crystallographic studies suggest the catenane is capable of stabilising a sodium chloride ion-pair in a host-separated binding mode. Modifications to the [3]catenane design with the aim of improving its yield and ion recognition capabilities are presented.</p>
<p><strong>Chapter 5</strong> presents the main conclusions of this thesis.</p>
<p><strong>Chapter 6</strong> details the experimental procedures employed in this work, including synthetic protocols and characterisation of novel compounds.</p> |
| first_indexed | 2024-09-25T04:32:59Z |
| format | Thesis |
| id | oxford-uuid:1e2a1834-a5e5-4655-b7ee-a8f5a8ccea7f |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-09-25T04:32:59Z |
| publishDate | 2024 |
| record_format | dspace |
| spelling | oxford-uuid:1e2a1834-a5e5-4655-b7ee-a8f5a8ccea7f2024-09-10T08:51:50ZHalogen bonding interlocked host systems for recognition and sensing of charged guestsThesishttp://purl.org/coar/resource_type/c_db06uuid:1e2a1834-a5e5-4655-b7ee-a8f5a8ccea7fSupramoleclar ChemistryEnglishHyrax Deposit2024Tay, HMBeer, P<p>This thesis describes the development of cation and anion template-directed methodologies to prepare interlocked host molecules for the recognition of charged guests, principally anions and ion-pairs. The use of halogen bonding motifs as both anion templating and binding motifs is explored as a strategy to enhance the ion recognition properties of the interlocked hosts.</p> <p><strong>Chapter 1</strong> introduces the field of supramolecular chemistry and outlines the key principles underlying host-guest chemistry. Advances in the design of receptors for anion and ion-pair recognition are reviewed, with a particular focus on receptors utilising halogen bonding (XB) interactions. The template-directed preparation of mechanically interlocked molecules and their applications in host-guest recognition and sensing is discussed.</p> <p><strong>Chapter 2</strong> describes the ion-pair binding properties of neutral heteroditopic XB catenanes and rotaxanes prepared via an alkali metal cation template-directed approach. The binding of alkali metal cations, halide anions and their respective ion-pairs by the interlocked hosts is investigated by 1H NMR titration studies, revealing significant positive cooperativity between cation and anion binding events. Crystallographic analysis is used to probe the binding modes and stoichiometries of the catenane receptors. The ion-pair binding capabilities of the receptors are also exploited for the selective solid-liquid extraction of alkali metal halide salts.</p> <p><strong>Chapter 3</strong> describes the use of a novel chloride anion template-directed strategy to prepare neutral XB [2]catenane and [2]rotaxane interlocked host molecules. 1H NMR binding studies of the host molecules in aqueous-acetone solvent mixtures demonstrate a mechanical bond induced anti-Hofmeister halide anion binding preference, which is exploited to develop selective interlocked systems for anion membrane transport and sensing.</p> <p><strong>Chapter 4</strong> details the use of orthogonal cation and anion template-directed strategies to prepare a heteroditopic [3]catenane possessing interlocked binding cavities for both the cationic and anionic guests. Crystallographic studies suggest the catenane is capable of stabilising a sodium chloride ion-pair in a host-separated binding mode. Modifications to the [3]catenane design with the aim of improving its yield and ion recognition capabilities are presented.</p> <p><strong>Chapter 5</strong> presents the main conclusions of this thesis.</p> <p><strong>Chapter 6</strong> details the experimental procedures employed in this work, including synthetic protocols and characterisation of novel compounds.</p> |
| spellingShingle | Supramoleclar Chemistry Tay, HM Halogen bonding interlocked host systems for recognition and sensing of charged guests |
| title | Halogen bonding interlocked host systems for recognition and sensing of charged guests |
| title_full | Halogen bonding interlocked host systems for recognition and sensing of charged guests |
| title_fullStr | Halogen bonding interlocked host systems for recognition and sensing of charged guests |
| title_full_unstemmed | Halogen bonding interlocked host systems for recognition and sensing of charged guests |
| title_short | Halogen bonding interlocked host systems for recognition and sensing of charged guests |
| title_sort | halogen bonding interlocked host systems for recognition and sensing of charged guests |
| topic | Supramoleclar Chemistry |
| work_keys_str_mv | AT tayhm halogenbondinginterlockedhostsystemsforrecognitionandsensingofchargedguests |