Electrochemical and Spectroelectrochemical Studies of Complexes with Multiple Redox Centers

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The electrochemical and spectroscopic properties of different types of complexes with multiple redox centers were investigated. Cyclic voltammetry was used as the main electrochemical technique along with thin-layer UV-visible and FTIR spectroelectrochemistry. The primary focus of this work was to elucidate the overall redox behavior of the compounds and to examine the site of electron transfer. Ligand binding reactions were also monitored by UV-visible spectroscopy and/or electrochemical titration methods. The examined electroactive compounds included: (i) free base corroles with nitro substituents at the β-pyrrole positions, (ii) β-nitro substituted iron corroles, (iii) bis-[PcRu(CO)][Ru2(ap)4(C≡CC5H4N)2]: a tetraruthenium complex containing two ruthenium(II) phthalocyanines and one metal-metal bonded diruthenium(III,III) unit, (iv) diruthenium complexes containing four symmetrical anionic bridging ligands and (v) copper(I) complexes with diethoxyphosphoryl-substituted 1,10-phenanthroline ligands.

Electrochemistry, Spectroelectrochemistry, Corroles, Diruthenium complexes, Phthalocyanines, Phenanthroline
Portions of this document appear in: Nardis, Sara, Manuela Stefanelli, Pruthviraj Mohite, Giuseppe Pomarico, Luca Tortora, Machima Manowong, Ping Chen et al. "β-Nitro derivatives of iron corrolates." Inorganic chemistry 51, no. 6 (2012): 3910-3920. And in: Stefanelli, Manuela, Giuseppe Pomarico, Luca Tortora, Sara Nardis, Frank R. Fronczek, Gregory T. McCandless, Kevin M. Smith et al. "β-Nitro-5, 10, 15-tritolylcorroles." Inorganic chemistry 51, no. 12 (2012): 6928-6942. And in: Manowong, M.; Van Caemelbecke, E.; Rodríguez-Morgade, M. S.; Bear, J. L.; Kadish, K. M.; Torres, T. J. Porphyrins and Phthalocyanines 2014, 18, 1-9. And in: Mitrofanov, Alexander, Machima Manowong, Yoann Rousselin, Stéphane Brandès, Roger Guilard, Alla Bessmertnykh‐Lemeune, Ping Chen, Karl M. Kadish, Nataliya Goulioukina, and Irina Beletskaya. "Structural and Electrochemical Studies of Copper (I) Complexes with Diethoxyphosphoryl‐1, 10‐phenanthrolines." European Journal of Inorganic Chemistry 2014, no. 21 (2014): 3370-3386.