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Title: Structure and mechanism in macrocyclic systems
Author: Labat, Gaël Charles
ISNI:       0000 0001 3603 514X
Awarding Body: Nottingham Trent University
Current Institution: Nottingham Trent University
Date of Award: 2002
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The aim of this work was to produce a range of crystalline thiophene-based macrocycles and macrocyclic complexes and to investigate their structure-property relationships. This involved studies of the structures of macrocycles and also their mechanism of complexation with metals including nickel, copper, aluminium, and silver. The macrocycles and relevant complexes were prepared and crystallised from solution, and their structure-property relationships investigated by using X-ray crystallography and spectroscopy, in addition to theoretical calculations of molecular geometry and binding energy, and optimisation of molecular geometry using suites of molecular modelling programs. The results obtained showed that metal complexation did not always occur in macrocycle cavities of apparently optimum size and that in the case of silver the metal did not enter the macrocycle, but bonded externally to an electronegative atom from the ring. The infrared spectroscopy showed some peaks that were characteristic of the counterion (for example perchlorate and isocyanate), but it was also possible to identify some new peaks and some peak shifts due to complexation of the metal ions with the ligand (for example Al(III)-O). Moreover, the ¹H and ¹³C NMR spectroscopy revealed several significant peak shifts between the free ligands and the complexed ligand due to interactions between the ligand and the metal ion, which depend on through which atoms and how strongly the metal ion is complexed with the ligand.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Physical chemistry