Tuning the physical and optoelectronic properties of phosphorescent iridium(III) complexes : applications to organic semiconductor devices
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This thesis explores the design, synthesis and characterisation of iridium(III) complexes for optoelectronic applications; in particular, cationic [Ir(CˆN)₂(NˆN)]⁺-type emitters (where CˆN is an anionic bidentate cyclometalating ligand such as 2-phenylpyridinato, ppy, and NˆN is a neutral bidentate ligand such as 2,2’-bipyridine, bpy) for use in light-emitting electrochemical cells (LEECs). Design strategies aim to achieve high photoluminescence quantum yields (Φ[sub](PL)) for these complexes. Chapter 1 provides an overview of the fundamental photophysics of luminescent transition metal complexes, before reviewing state of the art iridium complexes employed in LEEC devices. Chapter 2 employs a combination of the electron-deficient 2,4-difluorophenylpyridine (dFppy) CˆN ligand and various functionalised biimidazole (biim) NˆN ligands. Within the family of different biim ligands the emission energy does not vary significantly, but the excited state kinetics di.er depending on the rigidity of the biim ligand. Combining the lead biim ligand with a sterically bulkier CˆN ligand gives an iridium complex that emits deep blue light with 90% Φ[sub](PL) in MeCN. Chapter 3 describes an approach to replacing the electrochemically unstable aryl carbon-fluorine bonds in dFppy, while maintaining the deep blue emission colour observed for the complexes in Chapter 2. Chapter 4 expands on the concept of rigid biim ligands to bibenzimidazoles (bibenz). Combining conjugated bibenz NˆN ligands with more conjugated CˆN ligands allows for the emission colour of these complexes to be tuned to the orange/red. The Φ[sub](PL) necessarily falls due to the energy gap law, but is nevertheless higher than values measured for reference complexes. Chapter 5 explores the use of an arylazoimidazole ligand with donor-acceptor intraligand charge transfer characteristics in order to red-shift the emission further. The resultant complex is poorly emissive, but shows a panchromic absorption profile and high molar absorptivity, which is unusual for iridium(III) complexes. The absorption profile can be tuned as a function of the protonation state of the imidazole.
Thesis, PhD Doctor of Philosophy
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