Self-Assembled Bilayers as an Anchoring Strategy: Catalysts, Chromophores, and Chromophore-Catalyst Assemblies.

Anchoring strategies for immobilization of molecular catalysts, chromophores, and chromophore-catalyst assemblies on electrode surfaces play an important role in solar energy conversion devices such as dye-sensitized solar cells and dye-sensitized photoelectrosynthesis cells. They are also important in interfacial studies with surface-bound molecules including electron-transfer dynamics and mechanistic studies related to small molecule activation catalysis. Significant progress has been made in this area, but many challenges remain in terms of stability, synthetic complexity, and versatility. We report here a new anchoring strategy based on self-assembled bilayers. This strategy takes advantage of noncovalent interactions between long alkyl chains chemically bound to a metal-oxide electrode surface and long alkyl chains on the molecule being anchored. The new methodology is applicable to the heterogenization of both catalysts and chromophores as well as to the in situ "synthesis" of chromophore-catalyst assemblies on the electrode surface.