Ultrafast, Light-Induced Electron Transfer in a Perylene Diimide Chromophore-Donor Assembly on TiO2

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• 作者：M. Kyle Brennaman ; Michael R. Norris ; Melissa K. Gish ; Erik M. Grumstrup ; Leila Alibabaei ; Dennis L. Ashford ; Alexander M. Lapides ; John M. Papanikolas ; Joseph L. Templeton ; Thomas J. Meyer
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2015
• 出版时间：December 3, 2015
• 年：2015
• 卷：6
• 期：23
• 页码：4736-4742
• 全文大小：465K
• ISSN：1948-7185

文摘

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 ¹PDI* does not occur, but rather leads to the ultrafast formation of the redox-separated pair PDI^鈥?,PDI^{鈥⑩€?/sup>, which decays with complex kinetics (蟿₁ = 0.8 ps, 蟿₂ = 15 ps, and 蟿₃ = 1500 ps). With the added Fe(II) polypyridyl complex, rapid (<25 ps) oxidation of Fe(II) by the PDI鈥?,PDI鈥⑩€?/sup> redox pair occurs to give Fe(III),PDI鈥⑩€?/sup> persisting for >400 渭s in the film environment.}