Abstract
The focus of this thesis is the development of conjugated homo- and heterometallic polyyne complexes for which the opto-electronic properties may be tuned to provide potential applications in molecular electronic devices.Chapter 1 outlines the requirement of molecular systems for the development of the electronics industry, and describes the underlying chemistry of Pt-acetylide and {Mo2}-carboxylate systems that makes them promising materials in this respect.
Chapter 2 describes the development of ester-functionalised Pt-acetylide complexes, representing potential building blocks for complicated heterometallic frameworks. The relationship between the opto-electronic properties of these materials and the identity of their ligand systems is explored both spectroscopically and theoretically.
Chapter 3 outlines the development of a series of conjugated heterometallic frameworks via the systematic assembly of appropriate Pt-acetylide and {Mo2}carboxylate building blocks. The combinative effects of the two metal fragments on the properties of the materials are investigated spectroscopically and electrochemically and theoretical studies provide a greater understanding of the electronic structures of the novel species.
Chapter 4 describes the design and syntheses of novel ethynyl-functionalised bisamidine systems and their application as bridging ligands in a series of Ru-bisamidinate complexes. The highly tuneable opto-electronic properties of these complexes are probed both spectroscopically and electrochemically and interesting solid-state packing interactions are explored.
Chapter 5 illustrates the diverse coordination chemistry of N-heterocyclic carbenes towards {Mo2} carboxylate dimers. Structural analyses provide an important insight into the different coordination modes that are available by tuning the steric demands of the carbene and reveal rare Mo-Aryl π-interactions. Spectroscopic analyses are implemented to illustrate the ability to tune the energy of the Mo2δ→Mo2δ* electronic transition.
Chapter 6 presents preliminary results from the TR-IR spectroscopic analyses of several Pt-ethynyl-ester complexes and a mixed Pt-{Mo2} system. Attempts are made to identify ultra-fast charge transfer and charge redistribution processes following photo-excitation from the ground state.
| Date of Award | 1 Oct 2013 |
|---|---|
| Original language | English |
| Awarding Institution |
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| Supervisor | Paul Raithby (Supervisor) & Andrew Johnson (Supervisor) |
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