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Recent advances in our mechanistic understanding of dye-sensitized electron transfer reactions occurring at metal oxide interfaces are described. These advances were enabled by the advent of mesoporous thin films, comprised of anatase TiO2 nanocrystallites, that are amenable to spectroscopic and electrochemical characterization in unprecedented molecular-level detail. The metal-to-ligand charge transfer (MLCT) excited states of Ru polypyridyl compounds serve as the dye sensitizers. Excited-state injection often occurs on ultrafast timescales with yields that can be tuned from unity to near zero through modification of the sensitizer or the electrolyte composition. Transport of the injected electron and the oxidized sensitizer (hole-hopping) are both operative in the composite mechanism for charge recombination between the injected electron and the oxidized sensitizer. Sensitizers that contain a pendant electron donor, as well as core/shell TiO2/SnO2 nanostructures, often prolong the lifetime of the injected electron and provide fundamental insights into adiabatic and non-adiabatic electron transfer mechanisms. Regeneration of the oxidized sensitizer by iodide is enhanced through halogen bonding, orbital pathways, and ion-pairing. A substantial ~ 10 MV cm–1 electric field is created by electron injection into TiO2 nanocrystallites that induces ion migration, reports on the sensitizer dipole orientation, and (in some cases) re-orients or flips the sensitizer. Dye-sensitized conductive oxides also promote long-lived charge separation with bias dependent kinetics that provide insights into the reorganization energies associated with electron and proton-coupled electron transfer in the electric double layer.

Hu, K.; Sampaio, R. N.; Schneider, J.; Troian-Gautier, L.; Meyer, G. J. Perspectives on Dye Sensitization of Nanocrystalline Mesoporous Thin Films. J. Am. Chem. Soc. 2020, 142 (38), 16099-16116.

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