Electrochemical and Chemical Investigations of Various Substituted Porphyrins, Chlorins and Porphyrazines



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In this dissertation, by studying the electrochemistry and spectroelectrochemistry of three types of macrocycles: β-substituted, meso-substituted and/or fused porphyrins, chlorins and porphyrazines derivatives in a variety of non-aqueous media, the substituent, macrocycle, metal center, solvent condition, temperature and supporting electrolyte effects on the electrochemical and chemical behavior of these three types of macrocycles are investigated. Electrochemically or chemically synthesized products are also detected with different added anions, bases, or acids. Here are the key findings described in this dissertation: the electrochemically and chemically driven interconversion between the Ni(II) hydroxyphenylporphyrin and a reduced porphodimethene or oxidized porphyrin-like product, porpho-5,15-bis-paraquinone methide is seen; up to four facile reversible ring-centered reductions generating chlorin tetraanions are observed for the difused chlorins for the first time; strong hydrogen bonded dimers which exhibit mutiple reductions due to electronic communication between the two porphyrin -ring systems are observed; by changing the size of π-ring systems, adding electron withdrawing/donating substituents or ligating metal centers with different ligands, the redox potentials can be tuned accordingly.



Electrochemistry, Spectroelectrochemistry, Porphyrins, Chlorins, Porphyrazines


Portions of this document appear in: Cong, Lei, Mandeep K. Chahal, Ryan Osterloh, Muniappan Sankar, and Karl M. Kadish. "Synthesis, Electrochemistry, and Reversible Interconversion among Perhalogenated Hydroxyphenyl Ni (II) Porphyrins, Porphodimethenes, and Porpho-5, 15-bis-paraquinone Methide." Inorganic chemistry 58, no. 21 (2019): 14361-14376. And in: Chaudhri, Nivedita, Lei Cong, Nitika Grover, Wenqian Shan, Kumari Anshul, Muniappan Sankar, and Karl M. Kadish. "Synthesis and Electrochemical Characterization of Acetylacetone (acac) and Ethyl Acetate (EA) Appended β-Trisubstituted Push–Pull Porphyrins: Formation of Electronically Communicating Porphyrin Dimers." Inorganic Chemistry 57, no. 21 (2018): 13213-13224. And in: Saltini, Giulia, Lei Cong, Maria Pia Donzello, Claudio Ercolani, Elisa Viola, Ida Pettiti, Pavel A. Stuzhin, and Karl M. Kadish. "Tetra-2, 3-pyrazinoporphyrazines with Peripherally Appended Pyridine Rings. 20. Mono-and Pentanuclear AlIII and GaIII Complexes: Synthesis and Physicochemical and Photoactivity Studies." Inorganic chemistry (2019). And in: Sciscione, Fabiola, Lei Cong, Maria Pia Donzello, Elisa Viola, Claudio Ercolani, and Karl M. Kadish. "Octakis (2-pyridyl) porphyrazine and Its Neutral Metal Derivatives: UV–Visible Spectral, Electrochemical, and Photoactivity Studies." Inorganic chemistry 56, no. 10 (2017): 5813-5826.