| In this dissertation, the redox and UV-visible spectroscopic properties of a series of porphyrin family compounds, from building blocks of porphyrins to extended porphyrin-like molecule linkages, are investigated systematically in nonaqueous solvents. Open-chain oligopyrroles, which include bi-, ter-, and quaterpyrroles, are studied in dichloromethane by means of cyclic voltammetry and thin-layer spectroelectrochemistry. Protonation reactions are coupled with the electron transfer processes of these pyrroles oxidation to the cation radical. The di-substituted metalloporphyrins investigated in this dissertation are represented by (5, 15-diphenyl P)M and (5, 10-ditolyl P)M, where P = the parent porphyrin macrocycle and M = 2H, ZnII, CuII and NiII. Each of these porphyrins with reduced symmetry undergoes two one-electron reversible reductions and one or more irreversible oxidations following chemical reactions in benzonitrile, dichloromethane and pyridine. The electrochemical, spectroelectrochemical and catalytical properties of di-substituted Ni(II) porphyrins are also investigated compared with tetra-substituted Ni(II) porphyrins to demonstrate how the electron transfer sites depend on the structures. Tetra-substituted porphyrins can be linked to a cobaltabisdicarbollide group by different linkers for the purpose of boron neutral capture therapy. Compounds in the porphyrin family, such as chlorins and bacteriochlorins, also can be linked with several functional groups for use in photodynamic therapy. These extended porphyrin-like molecules linkage conjugates were characterized in benzonitrile and the results of this study indicate that the interaction between the porphyrin and other functional groups can affect the electron transfer sites of the different reactions. |
