Mechanistic Insights into the Charge Transfer Dynamics of Photocatalytic Water Oxidation at the Lipid Bilayer-Water Interface.

Photosystem II, the natural water-oxidizing system, is a large protein complex embedded in a phospholipid membrane. A much simpler system for photocatalytic water oxidation consists of liposomes functionalized with amphiphilic ruthenium(II)-tris-bipyridine photosensitizer (PS) and 6,6'-dicarboxylato-2,2'-bipyridine-ruthenium(II) catalysts (Cat) with a water-soluble sacrificial electron acceptor (NaSO). However, the effect of embedding this photocatalytic system in liposome membranes on the mechanism of photocatalytic water oxidation was not well understood. Here, several phenomena have been identified by spectroscopic tools, which explain the drastically different kinetics of water photo-oxidizing liposomes, compared with analogous homogeneous systems. First, the oxidative quenching of photoexcited PS* by SO at the liposome surface occurs solely via static quenching, while dynamic quenching is observed for the homogeneous system. Moreover, the charge separation efficiency after the quenching reaction is much smaller than unity, in contrast to the quantitative generation of PS in homogeneous solution. In parallel, the high local concentration of the membrane-bound PS induces self-quenching at 10:1-40:1 molar lipid-PS ratios. Finally, while the hole transfer from PS to catalyst is rather fast in homogeneous solution ( > 1 × 10 s at [catalyst] > 50 μM), in liposomes at pH = 4, the reaction is rather slow ( ≈ 17 s for 5 μM catalyst in 100 μM DMPC lipid). Overall, the better understanding of these productive and unproductive pathways explains what limits the rate of photocatalytic water oxidation in liposomal vs homogeneous systems, which is required for future optimization of light-driven catalysis within self-assembled lipid interfaces.