Surface-Attached [(NC)5Fe(CN)Pt(NH3)4(NC)Fe(CN)5]4−: A Study in the Electrochemical and Photochemical Control of Surface Morphology

Brian W. Pfennig, Andrew Bruce Bocarsly

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16 Scopus citations

Abstract

The [Pt(NH3)4]24+ salt of [(NC)5FeII(CN)PtIV(NH3)4(NC)FeII(CN)5]4− (I) was electrochemically derivatized on a Ni surface by anodic precipitation as the Ni2+ analogue, Ni2I. The resulting electrode surface was characterized by diffuse-reflectance FTIR spectroscopy and cyclic voltammetry. The cyclic voltammetric response of this species was similar to that of the solution species and was found to be only slightly variant with intercalated cation. However, this noncrystalline surface could be photochemically modified to generate a nickel ferrocyanide lattice, which is electrochemically cation sensitive. The photoinduced crystallization process was monitored by parallel electrochemical and X-ray powder pattern experiments. A mechanism for this transformation is proposed. In a separate set of reactions, it was found that the complex of interest can be electropolymerized onto an inert electrode surface. This process is believed to occur via oxidation of the “[FeIIPt,IVFeII]4−” anion to form the “[FeIIIPtIVFeIII]2−” dianion, which in turn oxidizes one of the Pt(II) counterions to form the polymeric species “[FeIIPtIV]n.” The spectroscopy and electrochemistry of the polymeric species is discussed.

Original languageEnglish (US)
Pages (from-to)666-672
Number of pages7
JournalInorganic Chemistry
Volume30
Issue number4
DOIs
StatePublished - Feb 1 1991

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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