Surface-Confined Ruthenium Complexes Bearing Benzimidazole Derivatives: Toward Functional Devices

Substitutionally inert ruthenium complexes bearing benzimidazole derivatives have unique electrochemical and photochemical properties. In particular, proton coupled electron transfer (PCET) in ruthenium–benzimidazole complexes leads to rich redox chemistry, which allows e.g. the tuning of redox potentials or switching by deprotonation. Using the background knowledge from acquired from their solution-state chemistry, Ru complexes immobilized on electrode surfaces have been developed and these offer new research directions toward functional molecular devices. The integration of surface-immobilized redox-active Ru complexes with multilayer assemblies via the layer-by-layer (LbL) metal coordination method on ITO electrodes provides new types of functionality. To control the molecular orientation of the complexes on the ITO surface, free-standing tetrapodal phosphonic acid anchor groups were incorporated into tridentate 2,6-bis(benzimidazole-2-yl)pyridine or benzene ligands. The use of the LbL layer growth method also enables “coordination programming” to fabricate multilayered films, as a variety of Ru complexes with different redox potentials and pKa values are available for incorporation into homo- and heterolayer films. Based on this strategy, many functional devices, such as scalable redox capacitors for energy storage, photo-responsive memory devices, proton rocking-chair-type redox capacitors, and protonic memristor devices have been successfully fabricated. Further applications of anchored Ru complexes in photoredox catalysis and dye-sensitized solar cells may be possible. Therefore, surface-confined Ru complexes exhibit great potential to contribute to the development of advanced functional molecular devices.