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Title: Orbital interactions
Author: Pascoe, Dominic James
ISNI:       0000 0004 7654 4741
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2018
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It is widely accepted that the sharing of electrons constitutes a bond. Conversely, molecular interactions that do not involve electron transfer, such as van der Waals forces and electrostatics are defined as "non-bonding" or "non-covalent" interactions. More recently computational and experimental observations have shown situations where the division between "bonding" and "non-bonding" interactions is blurred. One such class of interactions are known as σ-hole interactions. Chapter 1 provides a literature review of investigations into the nature of σ-hole interactions, highlighting the individual contributing factors. Chapter 2 provides a detailed analysis into the nature of chalcogen-bonding interactions. Synthetic molecular balances are employed for experimental measurements of conformational free energies in different solvents, facilitating a detailed examination of the energetics and associated solvent and substituent effects on chalcogen-bonding interactions. The chalcogen-bonding interactions examined were found to have surprisingly little solvent dependence. The independence of the conformational free energies on solvent polarity, polarisability and H-bond characteristics showed that electrostatic, solvophobic or dispersion forces were not dominant factors in accounting for the experimentally observed trends. A molecular orbital analysis provided a quantitative relationship between the experimental free energies and the molecular orbital energies, which was consistent with chalcogen-bonding interactions being dominated by an n→σ* orbital delocalisation. Chapters 3 and 4 both use the molecular orbital modelling approach established in Chapter 2 to investigate the potential partial covalency in H-bonding and carbonyl···carbonyl interactions. H-bonding is generally considered to be an electrostatically dominated interaction. However, computational results have suggested a partial covalent character in H-bonding. The molecular orbital analysis revealed an n→σ* electron delocalisation in all H-bonding systems evaluated. However, no quantitative correlation could be found with experimental free energies. Similarly, the nature of carbonyl···carbonyl interactions has been subject to debate, with electrostatic or an n→π* electron delocalisation having been proposed as the dominant factors. The molecular orbital analysis employed here showed that n→π* delocalisation was exceptionally geometry dependent. Studies of literature systems reveal that n→π* delocalisation contributes to overall stability of a range of systems, with a quantitative link between molecular orbital energy and conformational free energies.
Supervisor: Cockroft, Scott ; Lawrence, Andrew Sponsor: Engineering and Physical Sciences Research Council (EPSRC)
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: non-covalent interactions ; chalcogen interactions ; chalcogen···chalcogen interactions ; carbonyl interations ; bonding characteristics ; chalcogen-bonding interactions ; H-bonding ; orbital analysis