Development of a room temperature molecular electronics: Direct vs indirect metal complex synthesis
Cleary, Laura (2011) Development of a room temperature molecular electronics: Direct vs indirect metal complex synthesis. PhD thesis, Dublin City University.
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This thesis discusses the possibility of using molecular units as electronic devices as well as the synthesis of a number of such prototypes. This thesis also serves as a comparison between ‘direct’ (complexes as ligands/complexes as metals) and ‘indirect’ (on-complex) synthesis as a method of metal complex synthesis.
Chapter 1 introduces the theory behind molecular electronics and solar energy conversion as well as the applicability of transition metal complexes for this role. The target complexes to be synthesised as well as their methods of preparation are also introduced. The experimental methodology used to synthesize and characterize these complexes is detailed in chapter 2.
A number of ruthenium and osmium bis-bipyridyl metal complexes incorporating one phenanthroline type ligand have been synthesised using both direct and indirect synthetic methods and are discussed in Chapter 3. The synthesis of a series of ruthenium complexes containing two such ligands via an ‘indirect’ route is discussed in Chapter 4. These complexes are fully characterized via 1H-NMR, mass spectrometry and CHN with a discussion of their UV/vis and emission properties included.
The attempted synthesis of a series of dinuclear metal complexes, including two phenanthroline-thiophene type ligands (thimphen) using 3,5-bispyrid-2-yl-1,2,4- triazole as a bridging ligand is described in Chapter 5. A number of attempted synthetic routes for the dichloride starting material [Ru(thimphen)2Cl2] is also described.
The synthetic study of ruthenium(II) complexes containing the tetradentate ligands bis(2-pyridylmethyl)diiminoethane) (paen) and bis(2-pyridylmethyl)diiminopropane) (papn) is described in Chapter 6. A modified method for the synthesis of the starting materials [Ru(paen)Cl2] and [Ru(papn)Cl2] as well as a synthetic route for the metal complexes [Ru(paen)(P0P)Cl]+, [Ru(paen)(P0P)2]2+ and [Ru(papn)(P0P)2]2+ were developed. Again the complexes successfully synthesised are characterised by 1HNMR a discussion of their UV/vis and emission properties included.
Finally, the major conclusions drawn from this research and possible future work are also detailed.
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