Electrochemical and spectroscopic behavior of iron(III) porphyrazines in Langmuir-Schafer films

The Journal of Physical Chemistry. B
Gaetano GarramoneLudovico Valli

Abstract

Thin films of a newly synthesized iron(III) porphyrazine, LFeOESPz ( L = ClEtO, OESPz = ethylsulfanylporphyrazine), have been deposited by the Langmuir-Schafer (LS) technique (horizontal lifting) on ITO or gold substrates. Before deposition, the floating films have been investigated at the air-water interface by pressure/area per molecule (pi/ A) experiments, Brewster angle microscopy (BAM) and UV-vis reflection spectroscopy (RefSpec). The complex reacts with water subphase (pH 6.2) forming the mu-oxo dimer, which becomes the predominant component of the LS films ( LS-Fe) as indicated by optical, IR, XPS, and electrochemical data. LS-Fe multilayers exhibit, between open circuit potential (OCP) and +0.90 V (vs SCE), two independent peak pairs with formal potentials, E surf (I) and E surf(II) of +0.56 V and +0.78 V, respectively. According to dynamic voltammetric and coulometric experiments the peak pair at +0.56 V is attributed to one-electron process at the iron(III) centers on the monomer, while the peak pair at +0.78 V is associated to a four-electron process involving mu-oxo-dimer oligomers. LS-Fe films prove to be quite stable electrochemically between OCP and +0.90 V. The electrochemical stability decreases, however, when ...Continue Reading

References

Mar 1, 2003·The Journal of Organic Chemistry·Sven M BaumBrian M Hoffman
Jan 18, 2006·The Journal of Organic Chemistry·Matthew J FuchterAnthony G M Barrett
Sep 15, 2006·The Journal of Physical Chemistry. B·Peng SunChad A Mirkin
Aug 19, 2007·The Journal of Physical Chemistry. B·Anna SalvatiGiacomo Martini
Mar 21, 2008·Inorganic Chemistry·Alexander TheodoridisRudi van Eldik

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Citations

Jul 7, 2018·Langmuir : the ACS Journal of Surfaces and Colloids·Larissa A MaiorovaOskar I Koifman

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