Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers

Abstract Controlling the flow of electrical current at nanoscale typically requires complex top‐down approaches. Here, a bottom‐up approach is employed to demonstrate resistive switching within molecular wires that consist double‐helical metallopolymers and are constructed by self‐assembly. When material exposed an electric field, it determined ≈25% copper atoms oxidize from Cu I II , without rupture polymer chain. The ability sustain such high level oxidation unprecedented in copper‐based molecule: made possible here double helix compressing order satisfy new coordination geometry required . This mixed‐valence structure exhibits 10 4 ‐fold increase conductivity, which projected last on years. conductivity explained as being promoted creation, upon oxidation, partly filled orbitals aligned along array; long‐lasting nature change due structural rearrangement double‐helix, poses energetic barrier re‐reduction. work establishes helical platform for controlling currents nanoscale.