Redox Reactivity as the Controlling Element in Coordination Polymer Stereochemistry: Redox-Switched Growth Mechanism in the [FeII−CN−PtIV]n System

Coordination oligomers and polymers composed of [(CN)(5)Fe(II)-CN-Pt(IV)(NH(3))(4)] units have been synthesized. The oligomer growth mechanism is based on the oxidation state of the iron centers which can be specified either chemically or electrochemically to allow control over oligomer structure. Cyclic voltammetry is found to be a sensitive probe of oligomer and polymer structure. (13)C NMR is also shown to be a useful technique for characterizing the different geometric isomers. Thin films composed of [-(NC)(5)Fe(II)-CN-Pt(IV)(NH(3))(4)-](n)() were electropolymerized onto transparent indium tin oxide (ITO) electrode surfaces and characterized with regard to polymer morphology.