DEVELOPMENT OF REDOX-ACTIVE OPTICAL MESOSTRUCTURES AT CHEMICALLY-MODIFIED ELECTRODE INTERFACES

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)(5)Fe-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 M(n+) (M(n+) = Ni2+, Fe2+, Mn2+, Cr3+), M(n+) 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, M(n+) is incorporated into the interfacial lattice only at the irradiated regions. The film after M(n+) 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.