Here, the design, synthesis and characterisation and the optoelectronic properties of Ir(III) complexes for application in nonlinear optical and electroluminescent devices are described. The type of complexes varies from those of the form [Ir(C^N)2(N^N)]+ with conjugated and nonconjugated ligands (where C^N = cyclometalating ligand and N^N = neutral ligand) to those of the form [Ir(C^N^C)(N^N)Cl] (where C^N^C = tridentate tripod ligand). Chapter 1 gives an introduction into photophysics occurring in transition metal complexes and possible applications in visual displays. The background of nonlinear optical (NLO) properties and the use of transition metal complexes as NLO chromophores is described. In Chapter 2, the impact of the use of sterically congested cyclometalating ligands on the photoluminescence properties of cationic iridium(III) complexes and their performance in light-emitting electrochemical cells is investigated. Chapter 3 explores the use of electron donors on the cyclometalating ligand towards modulating the NLO properties of the complexes. Combining strongly electron-donating substituents on the C^N ligand and electron-accepting substituents on the N^N ligand results in strong NLO activity. Chapter 4 summarises a new series of cationic iridium(III) complexes bearing benzylpyridinato as cyclometalating ligands. The methylene spacer in the C^N ligands provides flexibility, resulting in two conformers. NMR studies combined with density functional theory (DFT) studies show how the fluxional behaviour is influenced by the choice of the ancillary ligand. In Chapter 5, Ir(III) complexes bearing an unusual nonconjugated bis(six-membered) tridentate tripod ligand of the form [Ir(C^N^C)(N^N)Cl] are introduced. Depending on the substitutions of the C^N^C ligand phosphorescence ranging from yellow to red was obtained. Substitution of the N^N results in a panchromatic NIR dye, suitable for DSSC applications. In Chapter 6, the concept of a nonconjugated ligand was expanded to the N^N ligand. Blue-green and sky-blue emission was obtained, demonstrating a strategy to successfully tune the emission to the blue.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:759342 |
| Date | January 2018 |
| Creators | Hierlinger, Claus |
| Contributors | Zysman-Colman, Eli ; Guerchais, Véronique |
| Publisher | University of St Andrews |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://hdl.handle.net/10023/16126 |
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