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Title: Ultrafast, Light-Induced Electron Transfer in a Perylene Diimide Chromophore-Donor Assembly on TiO 2

Abstract

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 [FeII(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•+,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.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1226090
Alternate Identifier(s):
OSTI ID: 1387241
Grant/Contract Number:  
SC0001011; AC05-06OR23100
Resource Type:
Published Article
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Name: Journal of Physical Chemistry Letters Journal Volume: 6 Journal Issue: 23; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; perylene bisimide; surface-bound; interfacial reaction; hole transfer; organic semiconductor

Citation Formats

Brennaman, M. Kyle, Norris, Michael R., Gish, Melissa K., Grumstrup, Erik M., Alibabaei, Leila, Ashford, Dennis L., Lapides, Alexander M., Papanikolas, John M., Templeton, Joseph L., and Meyer, Thomas J. Ultrafast, Light-Induced Electron Transfer in a Perylene Diimide Chromophore-Donor Assembly on TiO 2. United States: N. p., 2015. Web. doi:10.1021/acs.jpclett.5b02194.
Brennaman, M. Kyle, Norris, Michael R., Gish, Melissa K., Grumstrup, Erik M., Alibabaei, Leila, Ashford, Dennis L., Lapides, Alexander M., Papanikolas, John M., Templeton, Joseph L., & Meyer, Thomas J. Ultrafast, Light-Induced Electron Transfer in a Perylene Diimide Chromophore-Donor Assembly on TiO 2. United States. doi:10.1021/acs.jpclett.5b02194.
Brennaman, M. Kyle, Norris, Michael R., Gish, Melissa K., Grumstrup, Erik M., Alibabaei, Leila, Ashford, Dennis L., Lapides, Alexander M., Papanikolas, John M., Templeton, Joseph L., and Meyer, Thomas J. Thu . "Ultrafast, Light-Induced Electron Transfer in a Perylene Diimide Chromophore-Donor Assembly on TiO 2". United States. doi:10.1021/acs.jpclett.5b02194.
@article{osti_1226090,
title = {Ultrafast, Light-Induced Electron Transfer in a Perylene Diimide Chromophore-Donor Assembly on TiO 2},
author = {Brennaman, M. Kyle and Norris, Michael R. and Gish, Melissa K. and Grumstrup, Erik M. and Alibabaei, Leila and Ashford, Dennis L. and Lapides, Alexander M. and Papanikolas, John M. and Templeton, Joseph L. and Meyer, Thomas J.},
abstractNote = {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 [FeII(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•+,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.},
doi = {10.1021/acs.jpclett.5b02194},
journal = {Journal of Physical Chemistry Letters},
number = 23,
volume = 6,
place = {United States},
year = {2015},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acs.jpclett.5b02194

Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

Figures / Tables:

Chart 1 Chart 1: Structures of PDI-Based Assemblies TiO2-1 and TiO2-2

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.