An Ionic Twist on the Synthesis, Electrochemical and Spectroscopic Properties of Corroles, Porphyrins and Diruthenium Complexes

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This dissertation focuses on the utilizing electroanalytical methods to assess the properties of newly synthesized or electrosynthesized multi-redox active molecules such as metal-metal bonded diruthenium paddlewheel complexes, metallocorroles and porphyrins in non-aqueous and/or aqueous media. Several series of investigated compounds are examined by cyclic voltammetry, spectroelectrochemistry, NMR and UV-vis spectroscopy, and, in some cases, single crystal X-ray analysis. Properties of the neutral, reduced or oxidized forms of the examined species are utilized to determine the specific site of electron transfer (i.e. metal-, macrocycle- or substituent-centered) and an emphasis is placed on establishing electrochemical and/or other related linear free energy relationships between the various quantitative properties and empirical solvent or inductive parameters with the aim of offering powerful prediction tools intended to guide the direction of future work. In addition, the versatility of anions such as cyanide or fluoride to act as either complexing ligands or reductants via an anion induced electron transfer (AIET) is explored and a new diagnostic criterion is offered for determining ligand noninnocence in metallocorroles based on the AIET phenomenon.

Electrochemistry, Porphyrins, Corroles, Electrosynthesis
Portions of this document appear in: Osterloh, W. R.; Galindo, G.; Yates, M. J.; Van Caemelbecke, E.; Kadish, K. M., Synthesis, Structural and Physicochemical Properties of Water-Soluble Mixed-Ligand Diruthenium Complexes Containing Anilinopyridinate Bridging Ligands. Inorg. Chem. 2020, 59, 584-594; and in: Osterloh, W. R.; Desbois, N.; Quesneau, V.; Brandès, S.; Fleurat-Lessard, P.; Fang, Y.; Blondeau-Patissier, V.; Paolesse, R.; Gros, C. P.; Kadish, K. M., Old Dog, New Tricks: Innocent, Five-coordinate Cyanocobalt Corroles. Inorg. Chem. 2020, 59, 8562-8579; and in: Osterloh, W. R.; Fang, Y.; Desbois, N.; Naitana, M. L.; Brandés, S.; Pacquelet, S.; Gros, C. P.; Kadish, K. M., Here's looking at the reduction of noninnocent copper corroles via anion induced electron transfer. C. R. Chim. 2021, 24, 71-82.