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Electrochemistry and spectroelectrochemistry of 5,10,15,20-tetrakis(1,3-benzodioxole) porphyrin and its manganese and iron complexes

Geani Maria Ucoski

Departamento de Química, Universidade Federal do Paraná, Cx. Postal 19081, 81531-990 Curitiba PR, Brazil

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Shirley Nakagaki

Departamento de Química, Universidade Federal do Paraná, Cx. Postal 19081, 81531-990 Curitiba PR, Brazil

SPP full member in good standing.

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, and

Fábio Souza Nunes

Departamento de Química, Universidade Federal do Paraná, Cx. Postal 19081, 81531-990 Curitiba PR, Brazil

Corresponding author.

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https://doi.org/10.1142/S1088424614500473Cited by:8 (Source: Crossref)

Abstract

Cyclic voltammetry and thin-layer spectroelectrochemical properties of the free base 5,10,15,20-tetrakis(1,3-benzodioxole)porphyrin (H₂P), and its manganese and iron complexes (MnP and FeP, respectively) were studied in dichloromethane with tetra-butyl ammonium hexafluorophosphate (TBAPF₆) as supporting electrolyte. The free base undergoes two monoelectronic oxidations at +0.71 and +0.96 V vs. Ag/Ag⁺, corresponding to the formations of the π-cation radical and dication. Two reductions were observed at -1.53 and -1.87 V corresponding to the formation of π-anion and dianion species. The cyclic voltammograms of the Mn^III and Fe^III complexes also showed a reversible process centered in the metal ion with E_1/2 values at -0.61 and -0.59 V, respectively. In a typical experiment, in situ spectroelectrochemical response showed a decrease of the Soret band at 422 nm, a red shift of the Q-bands, and the new low intensity bands between 800–950 nm range. Structural features and spectroscopic assignments were proposed and discussed based on semi-empirical (molecular mechanics MMFF and ZINDO/S (Zerner method of intermediate neglect of differential overlap for spectroscopy) calculations.

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