Ru(II) polypridyl complexes investigated from the pico to the micro second domain
Henry, William (2006) Ru(II) polypridyl complexes investigated from the pico to the micro second domain. PhD thesis, Dublin City University.
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The present work probes the ground and excited state energy structures of a variety of Ru(II) complexes to better understanding the factors which affect their photo - chemical and - physical properties.
In the picosecond domain, ultrafast time resolved resonance Raman spectroscopy has been used to investigate the rate of formation of the thermally equilibrated excited (THEXI) state in [Ru(bpy)3]2+. These studies have shown that evolution of the THEXI state persists into the picosecond time range and is not complete on the femtosecond timescale, as previously suggested. These studies have also been extended to cover heteroleptic complexes and the effects of deuteriation and solvent.
Ru(II) complexes containing a 1,2,4 - triazole moiety have been investigated using a variety of techniques, including time correlated single photon counting, resonance Raman and transient absorption. At room temperature studies have shown the ability to control the electrochemical and photophysical properties through substitution of the triazole and alternating the symmetrical N N ligands.
Low temperature emission and single photon counting (on the microsecond timescale) measurements have shown the presence of two emissions for the 1,2,4 - triazole complexes containing a pyrazine moiety. These studies have highlighted the importance of electron délocalisation and excited state dipole, as well as the relative energies of the ligands, when controlling the excited state location.
Throughout the work deuteriation have been employed to considered effect with its application of particular importance to the Raman and excited state lifetime studies. Computational studies have also been used to augment the experimental work. These studies have reveal details about the energy level structures of dual emissive complexes while also highlighting some limitations of calculations preformed in an isolated environment.
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