Electrochemical and Surface Properties of Multilayer Films Based on a Ru²⁺ Metallodendrimer and the Mixed Addenda Dawson Heteropolyanion

The successful formation of organized multilayer assemblies, formed from the Dawson type mixed addenda heteropolyanion, [P 2 W 17 V IV O 62 ] 8− , and a Ru 2+ pentaerythritol based metallodendrimer, [RuDen] 8+ , has been achieved on carbon electrode surfaces. Cyclic voltammetric studies of the assembly across a wide pH domain, namely, 2 to 7 was possible. Upon redox switching, the redox couples associated with the Ru III/II redox system, of the cationic metallodendrimer, and both the V IV/V and the tungsten‐oxo framework of the heteropolyanion, were clearly evident. The multilayer assembly exhibited good stability towards both redox cycling and soaking over extended periods of time in aqueous buffer solutions. In addition, the constructed multilayer films were found to be quite compact in nature. The films were further characterized by X‐ray photoelectron spectroscopy (XPS) to determine their elemental composition. Surface morphology of the multilayer films was determined by atomic force microscopy (AFM). The electrocatalytic reduction of iodate by the multilayer film was also investigated.