Redox-activity and self-organization of iron-porphyrin monolayers at a copper/electrolyte interface

The Journal of Chemical Physics
Thanh Hai Phan, Klaus Wandelt

Abstract

The electrochemical behaviour and molecular structure of a layer of water-soluble 5,10,15,20-Tetrakis-(N-methyl-4-pyridyl)-porphyrin-Fe(III) pentatosylate, abbreviated as FeTMPyP, on a chloride modified Cu(100) electrode surface were investigated by means of cyclic voltammetry (CV) and in-situ electrochemical scanning tunneling microscopy. Voltammetric results of HOPG in an electrolyte containing FeTMPyP molecules indicate three distinguishable redox steps involving both the central iron metal and the π-conjugated ring system. However, only the first two reduction steps are observable within the narrow potential window of CVs of Cu(100) measured in the same electrolyte. In the potential range below the first reduction peak, at which the [Fe(III)TMPyP](5+) molecules are reduced to the corresponding [Fe(II)TMPyP](4+) species, in-situ scanning tunneling microscopy (STM) images revealed, for the first time, a highly ordered adlayer of this reduced porphyrin species on the chloride terminated Cu(100) surface. The ordered adlayer exhibits a (quasi)square unit cell with the lattice vectors |a→2|=|b→2|=1.53±0.1 nm and an angle of 93° ± 2° between them. A model is proposed based on the STM observation illustrating the arrangement of the...Continue Reading

References

Mar 14, 2002·Chemical Reviews·O M Magnussen
Oct 3, 2002·Journal of the American Chemical Society·Yufan HeEric Borguet
Oct 9, 2002·Journal of Computational Chemistry·Meng-Sheng Liao, Steve Scheiner
Jan 11, 2007·Langmuir : the ACS Journal of Surfaces and Colloids·Soichiro YoshimotoKingo Itaya
Aug 12, 2009·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Tobias N KraussYutaka Wakayama
Feb 27, 2013·International Journal of Molecular Sciences·Thanh Hai Phan, Klaus Wandelt

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