This dissertation describes photocoulometric and AC impedance studies of dye-modified electrodes. The photocoulometric technique allowed photoelectrochemical phenomena to be observed without mass transport effects. These measurements confirmed the photoconductive properties of monomeric silicon phthalocyanine dye. They also showed that the photo-assisted oxidation of hydroquinone to benzoquinone at n-tin oxide electrodes modified with this dye involved a cation dye intermediate with a lifetime of between 0.05 and 350 ns, with the rate limiting step being charge transport through the dye film or charge transfer across the interface between the dye and the substrate. AC impedance studies included Mott-Schottky measurements and faradaic impedance experiments on tin oxide and gold metallized plastic optically transparent electrodes. They also examined the substrates modified with monomeric silicon phthalocyanine and chloro-gallium phthalocyanine. The Mott-Schottky measurement procedure was free of systematic errors that affected other published work, and the results of these measurements were consistent with those found by independent methods. The faradaic impedance technique was applied to dye-modified electrodes for the first time. These studies found evidence for an adsorption or electrodeposition process in the oxidation of hydroquinone at these electrodes, and gave exchange current densities that were consistent with the values that were found by other methods.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Electrogenerated chemiluminescence (ECL) of new, highly fluorescent molecules was studied. Six novel, highly fluorescent, green emitters were synthesized by incorporating an acceptor group like 2,1,3-Benzothiadiazole between different donor groups. The structural effects on the electrochemical, spectroscopic, and ECL behavior are shown in detail. Stable electrochemistry and high PL quantum yield were observed. Most of the ECL was visible by the naked eye. Well-known, fluorescent, polyaromatic hydrocarbons (PAH), like 9,10-diphenylanthracene derivatives, pyrene, and anthracene were incorporated between two bulky fluorene derivative groups. The fluorene substitutions block the active positions of the PAH cores, permitting the formation of stable radical ions upon electrochemical oxidation or reduction. Such a tailoring led to increase electrochemical reversibility and tuning of the ECL wavelength. Fluorene-based DPA (FDF) is characterized by a highly efficient and stable blue-cyan color. Another interesting type of molecules was star-shaped structures. The effects of structure on the electrochemistry and spectroscopy of a series of star-shaped, rigid molecules was examined. T1-T4 is composed of oligofluorene arms with truxene as a central core basically there were weak donor and weak acceptors. The ECL quantum efficiency was near 80% for the long-arm T4. One of the interesting goals in ECL is to find ECL emitters in aqueous media. Organic nanoparticles (ONPs) were chosen to achieve this goal. An organic nanoparticle (ONPs) is still challenging area in nanoscience. The key factor of such a challenge comes from the difficulty to control the size and shape of the prepared nanoparticles. ONPs of common hydrocarbon ECL emitters like rubrene and 9,10-diphenylanthracene (DPA) were prepared in aqueous solution using a reprecipitation method. ECL of rubrene NPs was observed when tripropylamine (TPrA) was used as a coreactant, and weaker ECL of DPA NPs was observed when the oxalate ion was used as a coreactant. The ECL of ONPs in aqueous media may open a new field in ECL, allowing the exploration of more phenomena in organic nanoscience. Organic nanoparticle ECL (especially if one able to make small size to be diffused easily) has potential application as a tag for the analysis of biologically interesting molecules. / text

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The work described in this thesis is mainly concerned with the accurate measurement of redox potentials for a series of covalently linked porphyrin-quinone molecules (P-Q), in non-aqueous media. These compounds (synthesised by Prof. J.R. Bolton and co-workers of the University of Western Ontario, Canada) are of interest as models for the primary photochemical step in the photosynthetic process. The redox potentials were measured by cyclic voltammetry and differential pulse voltammetry. These electrochemical redox potentials were used to estimate the energy of the excited charge-separated state (P<SUP>.+</SUP>-Q<SUP>.-</SUP>), and confirm that this state is likely to be photochemically produced from the excited singlet state of P-Q rather than the triplet state. As a prelude and postscript to the studies of the P-Q compounds, the electrochemical behaviour of several related but simpler compounds, both porphyrins and quinones, is described. This includes an invesigation of the solvent dependence of quinone reduction potentials in non-aqueous media. A simple linear equation, based on Swain's A+B solvent parameters, is proposed as a means of predicting quinone reduction potentials in different solvents. Finally, the electrode kinetics of some simple metallorporphyrin oxidations are studied using an a.c. technique. A non-linear fitting routine was used to optimise the rate constant values obtained.