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An NMR study of molecular dynamics in organic crystalline compounds
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dc.contributor.advisor | Riddell, Frank G. | |
dc.contributor.author | Rogerson, Martin | |
dc.coverage.spatial | 173 p. | en_US |
dc.date.accessioned | 2018-07-02T11:51:54Z | |
dc.date.available | 2018-07-02T11:51:54Z | |
dc.date.issued | 1995 | |
dc.identifier.uri | https://hdl.handle.net/10023/14804 | |
dc.description.abstract | Using a combination of solid-state NMR techniques including Tip measurements, dynamic line shape analyses and 2D EXSY data, a variety of intramolecular motions including rotations of methyl, t-butyl, t-amyl, phenyl, trimethylammonium and trimethylphosphonium groups in a series of quaternary ammonium and phosphonium salts have been investigated. Where possible, activation parameters Ea, △G+/-, △H+/- and △S+/- have been derived. A range of values was recorded, especially for △S+/- which ranged from +75 JK⁻¹ mol⁻¹ for a phenyl group to -57 JK⁻¹ mol⁻¹for a t-butyl group. It was shown that ¹³p and ³¹p T1p measurements from CP/MAS spectra can give quantitative information on the kinetics of intramolecular motions that agree with line shape analysis. Recent work using X-ray crystallography has suggested that some derivatives of bicycle [3.3.1] nonane show evidence of conformational equilibria in the solid state. Using ¹³CP/MAS NMR, 22 derivatives of bicycle [3.3.1] nonane were studied, some at variable temperature. No evidence of conformational equilibria was observed in the chosen compounds. Solid-state NMR has been used to follow the kinetics of ring- chain tautomerism in a bicyclic tetrahydro-1,3-oxazine derivative. This was found to form initially the metastable chain on crystallisation, which then cyclises. The kinetics of the cyclisation were followed and the activation energy for the solid-state reaction was derived. In contrast to this, a related pyrimidine derivative has been found to form initially the metastable ring on cyclisation which quickly ring opens to the chain. | en_US |
dc.language.iso | en | en_US |
dc.publisher | University of St Andrews | |
dc.subject.lcc | QD273.R7 | |
dc.subject.lcsh | Organic electrochemistry | en |
dc.title | An NMR study of molecular dynamics in organic crystalline compounds | en_US |
dc.type | Thesis | en_US |
dc.contributor.sponsor | British Council | en_US |
dc.contributor.sponsor | Engineering and Physical Sciences Research Council (EPSRC) | en_US |
dc.contributor.sponsor | Hungary. Committee for Technological Development | en_US |
dc.type.qualificationlevel | Doctoral | en_US |
dc.type.qualificationname | PhD Doctor of Philosophy | en_US |
dc.publisher.institution | The University of St Andrews | en_US |
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