Surface-bound, perylenediimide (PDI)-based molecular assemblies have been synthesized on nanocrystalline TiO2 by reaction of a dianhydride with a surface-bound aniline and succinimide bonding. In a second step, the Fe(II) polypyridyl complex [Fe(II)(tpy-PhNH2)2](2+) was added to the outside of the film, also by succinimide bonding. Ultrafast transient absorption measurements in 0.1 M HClO4 reveal that electron injection into TiO2 by (1)PDI* does not occur, but rather leads to the ultrafast formation of the redox-separated pair PDI(•+),PDI(•-), which decays with complex kinetics (τ1 = 0.8 ps, τ2 = 15 ps, and τ3 = 1500 ps). With the added Fe(II) polypyridyl complex, rapid (<25 ps) oxidation of Fe(II) by the PDI(•+),PDI(•-) redox pair occurs to give Fe(III),PDI(•-) persisting for >400 μs in the film environment.
Keywords: hole transfer; interfacial reaction; organic semiconductor; perylene bisimide; surface-bound.