Photophysical characterization of a chromophore/water oxidation catalyst containing a layer-by-layer assembly on nanocrystalline TiO2 using ultrafast spectroscopy.

Femtosecond transient absorption spectroscopy is used to characterize the first photoactivation step in a chromophore/water oxidation catalyst assembly formed through a "layer-by-layer" approach. Assemblies incorporating both chromophores and catalysts are central to the function of dye-sensitized photoelectrosynthesis cells (DSPECs) for generating solar fuels. The chromophore, [Rua(II)](2+) = [Ru(pbpy)2(bpy)](2+), and water oxidation catalyst, [Rub(II)-OH2](2+) = [Ru(4,4'-(CH2PO3H2)2bpy)(Mebimpy)(H2O)](2+), where bpy = 2,2'-bipyridine, pbpy = 4,4'-(PO3H2)2bpy, and Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine), are arranged on nanocrystalline TiO2 via phosphonate-Zr(IV) coordination linkages. Analysis of the transient spectra of the assembly (denoted TiO2-[Rua(II)-Zr-Rub(II)-OH2](4+)) reveal that photoexcitation initiates electron injection, which is then followed by the transfer of the oxidative equivalent from the chromophore to the catalyst with a rate of kET = 5.9 × 10(9) s(-1) (τ = 170 ps). While the assembly, TiO2-[Rua(II)-Zr-Rub(II)-OH2](4+), has a near-unit efficiency for transfer of the oxidative equivalent to the catalyst, the overall efficiency of the system is only 43% due to nonproductive photoexcitation of the catalyst and nonunit efficiency for electron injection. The modular nature of the layer-by-layer system allows for variation of the light-harvesting chromophore and water oxidation catalyst for future studies to increase the overall efficiency.