Photodriven water oxidation initiated by a surface bound chromophore-donor-catalyst assembly

In photosynthesis, solar energy is used to produce solar fuels in the form of new chemical bonds. A critical step to mimic photosystem II (PS II), a key protein in nature's photosynthesis, for artificial photosynthesis is designing devices for efficient light-driven water oxidation. Here, we describe a single molecular assembly electrode that duplicates the key components of PSII. It consists of a polypyridyl light absorber, chemically linked to an intermediate electron donor, with a molecular-based water oxidation catalyst on a SnO 2 /TiO 2 core/shell electrode. The synthetic device mimics PSII in achieving sustained, light-driven water oxidation catalysis. It highlights the value of the tyrosine-histidine pair in PSII in achieving efficient water oxidation catalysis in artificial photosynthetic devices. We describe a single molecular assembly electrode that mimics PSII. Flash photolysis revealed the electron transfer steps between chromophore light absorption and the creation and storage of redox equivalents in the catalyst for water oxidation.