Charge Transport through Organic Molecular Wires Embedded in Ultrathin Insulating Inorganic Layer

Dense phase silica layers with thickness of a few nanometers featuring embedded organic molecular wires of type p-oligo(phenylenevinylene) are shown by visible light sensitized electrochemical measurements to transport charges across the insulating membrane. We find that such hybrid materials combination allows electronic charge transport only through the wires, while blocking molecular transport. Embodiment of the wire molecules in the silica was accomplished by atomic layer deposition under mild temperature conditions. Grown on Co oxide films for water oxidation, with the wire molecules covalently anchored on the oxide surface, the layer functions as a proton conducting separation membrane. Characterization by XPS, FT-IR and STEM/EDX confirms the integrity of the silica-encapsulated organic wires. Cyclic voltammetry with redox couple of selected potential relative to the energy levels of the wire molecules shows that the membrane is free of pinholes. The new type of membrane allows separation of incompatible redox reaction environments on the length scale of nanometers while enabling controlled electron transport between them. This opens up the coupling of carbon dioxide reduction with water oxidation, the essential reactions of artificial photosynthesis, in an integrated nanoscale photosystem.