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

doi:10.1021/ic00004a014

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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Abstract

The [Pt(NH₃)₄]2⁴⁺ salt of [(NC)₅Fe^II(CN)Pt^IV(NH₃)₄(NC)Fe^II(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 “[Fe^IIPt^,IVFeII]⁴⁻” anion to form the “[Fe^IIIPt^IVFe^III]²−” dianion, which in turn oxidizes one of the Pt(II) counterions to form the polymeric species “[Fe^IIPt^IV]_n.” The spectroscopy and electrochemistry of the polymeric species is discussed.

Original language	English (US)
Pages (from-to)	666-672
Number of pages	7
Journal	Inorganic Chemistry
Volume	30
Issue number	4
DOIs	https://doi.org/10.1021/ic00004a014
State	Published - Feb 1 1991

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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

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.",

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year = "1991",

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AU - Bocarsly, Andrew Bruce

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N2 - 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.

AB - 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.

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

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