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dc.contributor.advisorBuck, Manfred
dc.contributor.authorAitchison, Hannah
dc.coverage.spatialxii, 231 p.en_US
dc.description.abstractExploiting coordination bonding of aromatic carboxylic acids at metal surfaces, this thesis explores new directions in the design and application of self-assembled monolayers (SAMs). The SAMs are investigated using a multi-technique approach comprising of a complementary combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. In addition, the X-ray standing wave technique (XSW) was used to characterise the substrates. The process of layer formation and the final structures of the SAMs are found to be strikingly dependent on the combination of molecule and substrate, which is discussed in terms of the intermolecular and molecule-substrate interactions, bonding geometries and symmetry of the organic molecules. This is illustrated by the dramatic difference between molecular adsorption on Ag and Cu for molecules such as biphenyl-3,4’,5-tricarboxylic acid and biphenyl-4-acetic acid. In the case of self-assembly on Cu, the molecule-substrate interactions play a decisive role in the resulting SAM structure, whereas on Ag, the intermolecular interactions dominate over the weaker molecule-substrate binding. This exploration of the balance of interactions that lead to the formation of these SAM structures lays the foundation for a systematic design of the structures and properties of aromatic carboxylic acid based monolayers. Finally, different applications and properties of some SAMs were investigated, namely coordination of a Pd(II) complex to a pyridine/pyrazole terminated molecule adsorbed on Ag. Evidence of coordination of Pd(II) to single molecules was provided by STM, XPS and NEXAFS spectroscopy. Additionally, controlled STM tip induced modification of local areas of a 1,3,5-tris(4-carboxyphenyl)benzene SAM on Ag was performed, opening an exciting prospect for nanoscale molecular manipulation.en_US
dc.publisherUniversity of St Andrews
dc.subjectSelf-assembled monolayersen_US
dc.subjectAromatic carboxylic aciden_US
dc.subjectScanning tunneling microscopyen_US
dc.subjectX-ray photoelectron spectroscopyen_US
dc.subjectNear-edge X-ray absorption fine structureen_US
dc.subjectX-ray standing wave spectroscopyen_US
dc.subject.lcshMonomolecular filmsen_US
dc.subject.lcshSelf-assembly (Chemistry)en_US
dc.subject.lcshCarboxylic acidsen_US
dc.subject.lcshCoordination compoundsen_US
dc.titleSelf-assembly of monolayers of aromatic carboxylic acid molecules on silver and copper modified gold surfaces at the liquid-solid interfaceen_US
dc.type.qualificationnamePhD Doctor of Philosophyen_US
dc.publisher.institutionThe University of St Andrewsen_US
dc.rights.embargoreasonThesis restricted in accordance with University regulations. Print and electronic copy restricted until 28th April 2019, pending formal approvalen_US

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