A novel strategy to develop spatially structured polymer-modified electrodes is described. A semiconductor photoelectrode has been utilized as a template and the spatially restricted illumination has been employed as a means of controlling deposition areas of polymeric films. Arbitrary three dimensional control over the film growth process was achieved on such an electrode by relying on the unique semiconductor photoelectrochemical characteristics. Such spatially structured assemblies can undergo selective electrochemical and electrochromic changes in response to both light and the applied potential on the underlying semiconductor electrode. An alternative synthetic route via photosubstitution has also been explored to prepare the modified electrodes.;Investigations of novel polymerizable materials have been equally emphasized. The redox active metallopolymer film based on Re(CO);A group of 5-chlorophenanthroline complexes has been found to undergo reductive electropolymerization via the cleavage of the carbon-halide bond. Two possible reactions may exist for the generated radical: coupling with another radical to form a dimer or attacking an ordinary phenanthroline ligand. The latter reaction is not observed with 2,2;It has also been discovered that a series of phenanthroline complexes containing monodentate dipyridyl ligands can be oxidatively electropolymerized. More significantly, the polymerization process follows a redox mediated reaction mechanism; to our knowledge, no similar mechanism has been determined for electropolymerization. The presence of chelating pheanthroline ligands and ruthenium metal centers are two of the most important factors in controlling the extent of such reactions.
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