Novel Thienyl Dyes and related Metal Carbonyl Complexes
Boyle, Nicola (2010) Novel Thienyl Dyes and related Metal Carbonyl Complexes. PhD thesis, Dublin City University.
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Chapter one serves as an introduction to the principles and methods used throughout this
thesis. The principles of photophysics are discussed generally and also in relation to
porphyrins and dipyrromethenes. Potential applications for the novel thienyl dyes and related
metal carbonyl complexes synthesised are then presented. This is followed by an outline of
the techniques of laser flash photolysis, time-resolved infrared (TRIR) spectroscopy and time
correlated single photon counting.
Chapter two involves the study of thienyl porphyrins. This chapter begins with a literature
survey on the synthesis, photophysics and electrochemistry of thienyl porphyrin systems. The
synthesis of the porphyrins studied is given, followed by their photophysical and
electrochemical properties. The effect of the thienyl moiety on the ground state and excited
state properties of the porphyrin macrocycle is examined
Chapter three commences with a general introduction to Sonogashira-Hagihara type cross
coupling reactions and is followed by a literature survey on the synthesis and photochemistry
of thienyl based organometallic systems. The synthesis of the novel systems produced for this
study is then described and the photophysical properties are examined. Electrochemical data
are also presented. The photochemistry of the Co2(CO)6 complexes are examined by steady
state photolysis in the presence of a trapping ligand. Three of the complexes were studied by
TRIR on a picosecond timescale and the quantum yields of CO loss were determined at a
range of excitation wavelengths.
Chapter four commences with a literature survey focusing on the photophysics of pyridyl
porphyrins and related organometallic systems. The synthesis of the monopyridyltriphenyl
porphyrin and metal carbonyl derivatives produced for this study is described. The
photochemistry of the complexes was examined by pump and probe TRIR spectroscopy on a
Chapter five contains with a short literature review on the synthesis and photophysics of
dipyrromethanes and dipyrrin compounds. The synthesis of a series of substituted thienyl
dipyrromethanes, related dipyrrin complexes and corresponding dicobalt complexes is
presented. Preliminary photophysical measurements are discussed.
Finally chapter six discusses future work for chapters 3, 4 and 5.
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