This thesis explores the surface assembly of mechanically interlocked molecular architectures at gold surfaces for potential applications in molecular switches, anion sensing and stimuli (redox and optical) responsive molecular films. <b>Chapter One</b> introduces the field of mechanically interlocked molecules focusing on rotaxane and catenane surface assemblies in the form of single molecule thick self-assembled monolayers. A review of the surface-attached characteristics of mechanically interlocked molecules is given before exploring specific anion template directed strategies for their construction. The potential to incorporate both redox-active and optically-active functional groups within these mechanically interlocked molecules is also discussed. <b>Chapter Two</b> provides the experimental details and procedures employed in this thesis to characterise the molecular systems under investigation. <b>Chapter Three</b> introduces several surface characterisation techniques such as; ellipsometry, contact angle, X-ray reflectivity and X-ray photoelectron spectroscopy, with a particular focus of applying these tools to probe the surface co-conformation of switchable and interlocked molecules at surfaces. Electroanalytical techniques such as cyclic voltammetry, chronoamperometry and electrical impedance spectroscopy are also introduced. <b>Chapter Four</b> details the surface assembly of a series of ferrocene containing anion templated catenane self-assembled monolayers on gold. Detailed electrochemical and angle resolved X- ray photoelectron spectroscopy characterisation elucidates the co-conformation upon surface attachment. <b>Chapter Five</b> details the anion templated surface assembly of a redox-active rotaxane self- assembled monolayer on gold. Subsequent electroanalysis and X-ray photoelectron spectroscopy characterisation confirms the structural integrity of the film and a possible co- conformation at the surface is discussed. <b>Chapter Six</b> describes efforts towards constructing optically responsive hybrid d-f lanthanide containing mechanically interlocked molecules. Initial work focuses on switching characteristics of a redox switchable antennae and its ability to modulate the luminescence of a series of lanthanide complexes in solution. Subsequent surface attachment of the lanthanide complexes in the form of emissive self-assembled monolayers is also investigated.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:658400 |
| Date | January 2013 |
| Creators | Rahman, Habibur |
| Contributors | Davis, Jason |
| Publisher | University of Oxford |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://ora.ox.ac.uk/objects/uuid:1843aa56-2c40-4a97-9e2d-6ce600f9041f |
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