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Red emitting iridium(III) and rhenium(I) complexes developed for photonic applications

Elgar, Christopher 2021. Red emitting iridium(III) and rhenium(I) complexes developed for photonic applications. PhD Thesis, Cardiff University.
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This thesis outlines the design, synthesis, and characterisation of novel 2-arylquinoxalines and 2-arylquinoline fluorophores alongside their coordination with iridium(III) and rhenium(I) producing red emissive phosphors. The photophysical properties of the complexes are discussed, which could see possible applications in fields of LEECs and bioimaging. Chapter 2 describes the effects of different electron withdrawing and electron donating groups substituted into differing positions around the cyclometalated 2-phenylquinoxaline ligand and the subsequent results in the tuneability of emission wavelength of iridium(III) complexes. Chapter 3 outlines the effect of benzannulation in the cyclometalating ligand with a series of 2-(naphthyl)quinoxaline based cyclometalated iridium(III) complexes. The emission shifted to deeper red upon extending the conjugation, with mixed 3LC and 3MLCT character, differing in amounts between naphthalene isomers. Chapter 4 describes the cyclometalation of a series of 2-(naphthyl)quinoline cyclometalating ligands on iridium, describing the effects of substitution of the quinoline on the tuneability of emission. Detailed characterisation of the excited state has shown 1-napthyl complexes possess more 3MLCT character and can demonstrate successful TTA-UC with DPA. Chapter 5 describes the synthesis and characterisation of eight novel bidentate quinoline ligands, and their coordination to iridium as ancillary ligands. The result of detail the affects of extending the conjugation of the ancillary ligand, and how it is affecting the photophysical properties, with an emission range of 40 nm tuneability in 2-(naphth-2-yl)quinoline complexes. Chapter 6 takes the bidentate ligands from the previous chapter and chelates them with rhenium(I), forming neutral complexes, upon which they demonstrate 3MLCT emission from the solid state. Finally, Chapter 7 outlines the design, synthesis and characterisation of a cyclometalated iridium(III) complex incorporating a TTA-UC annihilator moiety. The complex is weakly upconverting in pure solution. The photophysical characterisation suggests back energy pathways between the annihilator moiety and the 3MLCT states dominate the desired upconversion fluorescence.

Item Type: Thesis (PhD)
Date Type: Completion
Status: Unpublished
Schools: Chemistry
Date of First Compliant Deposit: 9 November 2021
Last Modified: 09 Nov 2022 02:30

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