Development of Redox-Active Optical Mesostructures at Chemically Modified Electrode Interfaces

Ying Wu; Brian W. Pfennig; Andrew Bruce Bocarsly; Edward P. Vicenzi

doi:10.1021/ic00120a036

Development of Redox-Active Optical Mesostructures at Chemically Modified Electrode Interfaces

Ying Wu, Brian W. Pfennig, Andrew Bruce Bocarsly, Edward P. Vicenzi

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37 Scopus citations

Abstract

Polymeric films of [Fe^II(CN)₆-Pt^IV(NH₃)₄]_n were prepared on optically transparent indium tin oxide (ITO) electrode surfaces via oxidative polymerization of the monomer [Pt(NH₃)₄]₂[(NC)₅Fe-CN-Pt(NH₃)₄-NC-Fe(CN)₅]. Irradiation at 457 nm into the intervalence charge transfer band of the interfacial polymer causes the cleavage of bridging -CN- to Pt bonds, leading to the dissociation of polymeric film into shorter-chain [Fe-Pt]_n oligomers, [Pt(NH₃)₄]²⁺ and [Fe(CN)₆]³⁻. When photolysis is carried out with the modified interface immersed in an aqueous solution containing transition metal cations Mⁿ⁺ (Mⁿ⁺ = Ni²⁺, Fe²⁺, Mn²⁺, Cr³⁺), Mⁿ⁺ reacts with photogenerated [Fe(CN)₆]³⁻ complexes to form mixed metal cyanometalates of the form [M-NC-Fe(CN)₅]²⁻ on the electrode surface. As a result, Mⁿ⁺ is incorporated into the interfacial lattice only at the irradiated regions. The film after Mⁿ⁺ incorporation is different in color compared to the original [Fe-Pt]_n polymer film. Images may be developed on such a film by irradiating the sample through a mask. In this paper we report the formation and characterization of such multicomponent electrode surfaces. In addition, the potential applicability of these multicomponent electrodes as molecular electronic devices is discussed.

Original language	English (US)
Pages (from-to)	4262-4267
Number of pages	6
Journal	Inorganic Chemistry
Volume	34
Issue number	16
DOIs	https://doi.org/10.1021/ic00120a036
State	Published - Aug 1 1995

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{0c9211175f6f46edb219a7e7406a5f05,

title = "Development of Redox-Active Optical Mesostructures at Chemically Modified Electrode Interfaces",

abstract = "Polymeric films of [FeII(CN)6-PtIV(NH3)4]n were prepared on optically transparent indium tin oxide (ITO) electrode surfaces via oxidative polymerization of the monomer [Pt(NH3)4]2[(NC)5Fe-CN-Pt(NH3)4-NC-Fe(CN)5]. Irradiation at 457 nm into the intervalence charge transfer band of the interfacial polymer causes the cleavage of bridging -CN- to Pt bonds, leading to the dissociation of polymeric film into shorter-chain [Fe-Pt]n oligomers, [Pt(NH3)4]2+ and [Fe(CN)6]3−. When photolysis is carried out with the modified interface immersed in an aqueous solution containing transition metal cations Mn+ (Mn+ = Ni2+, Fe2+, Mn2+, Cr3+), Mn+ reacts with photogenerated [Fe(CN)6]3− complexes to form mixed metal cyanometalates of the form [M-NC-Fe(CN)5]2− on the electrode surface. As a result, Mn+ is incorporated into the interfacial lattice only at the irradiated regions. The film after Mn+ incorporation is different in color compared to the original [Fe-Pt]n polymer film. Images may be developed on such a film by irradiating the sample through a mask. In this paper we report the formation and characterization of such multicomponent electrode surfaces. In addition, the potential applicability of these multicomponent electrodes as molecular electronic devices is discussed.",

author = "Ying Wu and Pfennig, {Brian W.} and Bocarsly, {Andrew Bruce} and Vicenzi, {Edward P.}",

year = "1995",

month = aug,

day = "1",

doi = "10.1021/ic00120a036",

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pages = "4262--4267",

journal = "Inorganic Chemistry",

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publisher = "American Chemical Society",

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AU - Wu, Ying

AU - Pfennig, Brian W.

AU - Bocarsly, Andrew Bruce

AU - Vicenzi, Edward P.

PY - 1995/8/1

Y1 - 1995/8/1

N2 - Polymeric films of [FeII(CN)6-PtIV(NH3)4]n were prepared on optically transparent indium tin oxide (ITO) electrode surfaces via oxidative polymerization of the monomer [Pt(NH3)4]2[(NC)5Fe-CN-Pt(NH3)4-NC-Fe(CN)5]. Irradiation at 457 nm into the intervalence charge transfer band of the interfacial polymer causes the cleavage of bridging -CN- to Pt bonds, leading to the dissociation of polymeric film into shorter-chain [Fe-Pt]n oligomers, [Pt(NH3)4]2+ and [Fe(CN)6]3−. When photolysis is carried out with the modified interface immersed in an aqueous solution containing transition metal cations Mn+ (Mn+ = Ni2+, Fe2+, Mn2+, Cr3+), Mn+ reacts with photogenerated [Fe(CN)6]3− complexes to form mixed metal cyanometalates of the form [M-NC-Fe(CN)5]2− on the electrode surface. As a result, Mn+ is incorporated into the interfacial lattice only at the irradiated regions. The film after Mn+ incorporation is different in color compared to the original [Fe-Pt]n polymer film. Images may be developed on such a film by irradiating the sample through a mask. In this paper we report the formation and characterization of such multicomponent electrode surfaces. In addition, the potential applicability of these multicomponent electrodes as molecular electronic devices is discussed.

AB - Polymeric films of [FeII(CN)6-PtIV(NH3)4]n were prepared on optically transparent indium tin oxide (ITO) electrode surfaces via oxidative polymerization of the monomer [Pt(NH3)4]2[(NC)5Fe-CN-Pt(NH3)4-NC-Fe(CN)5]. Irradiation at 457 nm into the intervalence charge transfer band of the interfacial polymer causes the cleavage of bridging -CN- to Pt bonds, leading to the dissociation of polymeric film into shorter-chain [Fe-Pt]n oligomers, [Pt(NH3)4]2+ and [Fe(CN)6]3−. When photolysis is carried out with the modified interface immersed in an aqueous solution containing transition metal cations Mn+ (Mn+ = Ni2+, Fe2+, Mn2+, Cr3+), Mn+ reacts with photogenerated [Fe(CN)6]3− complexes to form mixed metal cyanometalates of the form [M-NC-Fe(CN)5]2− on the electrode surface. As a result, Mn+ is incorporated into the interfacial lattice only at the irradiated regions. The film after Mn+ incorporation is different in color compared to the original [Fe-Pt]n polymer film. Images may be developed on such a film by irradiating the sample through a mask. In this paper we report the formation and characterization of such multicomponent electrode surfaces. In addition, the potential applicability of these multicomponent electrodes as molecular electronic devices is discussed.

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Development of Redox-Active Optical Mesostructures at Chemically Modified Electrode Interfaces

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