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  Excitation Energy Transfer within Covalent Tetrahedral Perylenediimide Tetramers and Their Intermolecular Aggregates

Ramanan, C., Kim, C. H., Marks, T. J., & Wasielewski, M. R. (2014). Excitation Energy Transfer within Covalent Tetrahedral Perylenediimide Tetramers and Their Intermolecular Aggregates. The Journal of Physical Chemistry C, 118(30), 16941-16950. doi:10.1021/jp500475c.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0005-4A43-D Version Permalink: http://hdl.handle.net/21.11116/0000-0005-4A44-C
Genre: Journal Article

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Ramanan, Charusheela1, Author              
Kim, Chul Hoon, Author
Marks, Tobin J., Author
Wasielewski, Michael R., Author
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1Department of Chemistry, Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois, ou_persistent22              

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 Abstract: Perylenediimides (PDIs) offer a number of attractive characteristics as alternatives to fullerenes in organic photovoltaics (OPVs), including favorable orbital energetics, high extinction coefficients in the visible spectral region, photostability, and the capacity to self-assemble into ordered nanostructures. However, energy transfer followed by charge separation in PDI assemblies must kinetically out-compete excimer formation that limits OPV performance. We report on the excitation energy transfer (EET) rate in a covalently linked PDI tetramer in which the PDI chromophores are arranged in a tetrahedral geometry about a tetraphenyladamantane core. Transient absorption spectroscopy of the tetramer in CH2Cl2 reveals a laser intensity-dependent fast absorption decay component indicative of singlet?singlet annihilation resulting from intramolecular EET. Femtosecond fluorescence anisotropy measurements show that the EET time constant τ = 6 ps, which is similar to that predicted for a through-space F\"{o}}rster EET mechanism. Concentration-dependent steady-state spectroscopic studies reveal the formation of intermolecular aggregates of the tetramers in toluene. The aggregates are formed by cofacial π-stacking interactions between PDIs of neighboring tetramers. Transient absorption spectra of the aggregated tetramers in toluene solution demonstrate long-lived excited-state decay dynamics (τ ? 30 ns) in agreement with previous observations of PDI excimers. Perylenediimides (PDIs) offer a number of attractive characteristics as alternatives to fullerenes in organic photovoltaics (OPVs), including favorable orbital energetics, high extinction coefficients in the visible spectral region, photostability, and the capacity to self-assemble into ordered nanostructures. However, energy transfer followed by charge separation in PDI assemblies must kinetically out-compete excimer formation that limits OPV performance. We report on the excitation energy transfer (EET) rate in a covalently linked PDI tetramer in which the PDI chromophores are arranged in a tetrahedral geometry about a tetraphenyladamantane core. Transient absorption spectroscopy of the tetramer in CH2Cl2 reveals a laser intensity-dependent fast absorption decay component indicative of singlet?singlet annihilation resulting from intramolecular EET. Femtosecond fluorescence anisotropy measurements show that the EET time constant τ = 6 ps, which is similar to that predicted for a through-space F{\"{o}rster EET mechanism. Concentration-dependent steady-state spectroscopic studies reveal the formation of intermolecular aggregates of the tetramers in toluene. The aggregates are formed by cofacial π-stacking interactions between PDIs of neighboring tetramers. Transient absorption spectra of the aggregated tetramers in toluene solution demonstrate long-lived excited-state decay dynamics (τ ? 30 ns) in agreement with previous observations of PDI excimers.

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Language(s): eng - English
 Dates: 20142014
 Publication Status: Published in print
 Pages: -
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 Rev. Method: -
 Identifiers: DOI: 10.1021/jp500475c
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Title: The Journal of Physical Chemistry C
  Abbreviation : J. Phys. Chem. C
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 118 (30) Sequence Number: - Start / End Page: 16941 - 16950 Identifier: ISSN: 1932-7447
CoNE: https://pure.mpg.de/cone/journals/resource/954926947766