Thesis
Halogen and pnictogen bonding in host-guest chemistry
- Abstract:
-
This thesis describes the synthesis and characterisation of acyclic and macrocyclic receptors containing halogen- and pnictogen bonding motifs for the study of sigma(σ)-hole interactions for anion recognition, as well as the stabilisation of reactive halonium species through macrocyclic ligands.
Chapter 1 introduces supramolecular chemistry and the central concepts related to host-guest recognition and self-assembly. Different types of non-covalent interactions are discussed with a focus on sigma(σ)-hole interactions. Relevant literature examples related to anion recognition as well as interlocked host structures are furthermore presented.
Chapter 2 presents the synthesis of a series of antimony(III) and bismuth(III) based pnictogen bonding acyclic receptors, which were studied to elucidate the strength and selectivity of pnictogen bonding based anion recognition. The synthesis and study of mixed pnictogen- and halogen bonding tripodal receptors as well as mono- and bis-stibanotriazole based receptors is furthermore discussed.
Chapter 3 describes the synthesis of a series of halogen bonding lariat macrocycles incorporating ambidentate iodotriazole motifs into both the macrocycle and lariat arm. These were used to investigate anion and metal cation template directed synthetic routes for potential pseudo-[1]rotaxane assembly with the goal of constructing a functional [1]rotaxane capable of anion recognition through halogen bonding.
Chapter 4 details the study of four different bis-pyridine-based macrocycles for the complexation and stabilisation of reactive halonium cations. To this end, the solid-state structures of bromonium complexes as well as their parent Ag(I) and electronically related d10 Au(I) complexes are presented together with solution phase halonium cation 1H NMR ligand exchange studies, which reveal evidence for a macrocyclic effect for halonium guest species.
Chapter 5 presents a summary of the major conclusions from the research project and discusses future work.
Chapter 6 contains synthetic details and full characterisation of all novel compounds, as well as further details regarding 1H NMR titration experiment protocols and single-crystal XRD experiments.
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Authors
Contributors
- Institution:
- University of Oxford
- Division:
- MPLS
- Department:
- Chemistry
- Sub department:
- Inorganic Chemistry
- Role:
- Contributor
- Institution:
- University of Oxford
- Division:
- MPLS
- Department:
- Chemistry
- Sub department:
- Inorganic Chemistry
- Role:
- Supervisor
- Funding agency for:
- Kuhn, H
- Grant:
- EP/R513295/1
- Type of award:
- DPhil
- Level of award:
- Doctoral
- Awarding institution:
- University of Oxford
- Language:
-
English
- Keywords:
- Subjects:
- Deposit date:
-
2023-07-04
Terms of use
- Copyright holder:
- Kuhn, H
- Copyright date:
- 2022
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