Light‐Triggered Release of Trapped Charges in Molecular Assemblies

We demonstrate the mediation of charge transport and release in thin films and devices by shifting the redox properties of layers of metal complexes by light. The nanoscale surface arrangement of both photo‐ and electrochemically‐active components is essential for the function of the thin films. Layers of well‐defined ruthenium complexes on indium‐tin‐oxide electrodes provide electron‐transport channels that allow the electrochemical addressing of layers of isostructural cobalt complexes. These cobalt complexes are electrochemically inactive when assembled directly on transparent metal‐oxide electrodes. The interlayer of ruthenium complexes on such electrodes allows irreversible oxidation of the cobalt complexes. However, shifting the redox properties of the ruthenium complexes by excitation with light opens up an electron‐transport channel to reduce the cobalt complexes; hence releasing the trapped positive charges.