Electrochemistry of Aluminum Phthalocyanine: Solvent and Anion Effects on UV-Visible Spectra and Reduction Mechanisms.
The electrochemistry and UV-vis spectral properties of neutral and electroreduced Al(III) phthalocyanine, (Pc)AlCl, were characterized in four different nonaqueous solvents (THF, DMSO, DMF, and pyridine) containing tetra-n-butylammonium perchlorate, as well as in THF containing 0.4 M TBAP and the more strongly coordinating Cl(-), F(-), OH(-), or CN(-) anions added to solution in the form of a tetra-n-butylammonium salt. The initial phthalocyanine added to solution is represented as (Pc)AlCl, but the actual electroactive form of the compound varied as a function of both the solvent and type or number of bound anionic axial ligands. An uncharged (Pc)AlCl(THF) or (Pc)Al(CN)(THF) complex is present in THF solutions containing 0.4 M TBAP and excess Cl(-) or CN(-), while transient mu-oxo dimers are spectroscopically observed upon addition of OH(-) or F(-) to (Pc)AlCl(THF) in THF followed by the ultimate formation of stable six-coordinate anionic species represented as [(Pc)Al(OH)(2)](-) or [(Pc)AlF(2)](-). Each phthalocyanine undergoes three reversible one-electron additions at the conjugated Pc macrocycle within the negative potential limit of the solvent, and the UV-vis spectral changes obtained during the first two reductions were recorded in a thin-layer cell to evaluate the prevailing electron-transfer mechanisms.[1]References
- Electrochemistry of Aluminum Phthalocyanine: Solvent and Anion Effects on UV-Visible Spectra and Reduction Mechanisms. Ou, Z., Shen, J., Kadish, K.M. Inorganic chemistry (2006) [Pubmed]
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