Portland State University. Environmental Sciences and Resources Ph. D. Program
Carl C. Wamser
Date of Publication
Doctor of Philosophy (Ph.D.) in Environmental Sciences and Resources: Chemistry
Environmental Science and Management
Porphyrins, Oxidation-reduction reaction, Photovoltaic power generation
3, vii, 113 leaves: ill. (1 mounted col.) 28 cm.
Tetraphenylporphyrins can be used to absorb visible light and pass on their excitation energy to electron transfer agents. The purpose of this research has been to investigate our ability to understand and control the energetics of porphyrin derivatives in order to use their electron transfer ability to harness the energy of sunlight. Shifts in the redox (reduction and oxidation) potentials of tetraphenylporphyrins result from variations in the substituents attached at the para- position of the phenyl rings of tetraphenylporphyrins, as well as variations in the state of ionization of those substituents, and the solvent in which the reactions are carried out. To measure the effect these variations, results from cyclic voltammetric experiments were plotted versus literature values of Hammett substituent constants to confirm the validity of linear free energy relationships as a model of substituent effects. Solvent effects on reduction potentials were correlated using experimentally determined values of the empirical solvent parameter ET. Some specific conclusions are summarized. 1. The usefulness of linear free energy relationships in correlating variations in redox potentials with changes in substituent was confirmed with two exceptions. Two of the porphyrins were shown to undergo a different electrochemical oxidation mechanism than the remaining porphyrins, and another porphyrin was shown to be more difficult to reduce than predicted on the basis of its substituent constant. 2. Solvent effects, here investigated as the effect of added water on the reduction potential of tetraaminophenylporphyrin in DMSO, were demonstrated to correlate with the Dimroth-Reichardt solvent parameter, ET , determined experimentally for each water-DMSO mix. 3. Variations in the state of ionization of ionizable substituents such as carboxylic acid, amine, and hydroxyl substituents were shown to affect porphyrin electrochemistry mostly through the protonation of bulk, solution-phase porphyrin by added proton donor. An additional effect of added proton donor was noted in an alteration in the mechanism of reduction to include some of a different mechanism wherein reduced porphyrin is protonated in a chemical equilibrium and then further reduced electrochemically.
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Ransdell, Robert Arthur, "Solvent and Substituent Effects on the Redox Potentials of Several Substituted Tetraphenylporphyrins" (1991). Dissertations and Theses. Paper 1230.