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Title: Tuning Singlet Fission in π-Bridge-π Chromophores

Abstract

For this study, we have designed a series of pentacene dimers separated by homoconjugated or nonconjugated bridges that exhibit fast and efficient intramolecular singlet exciton fission (iSF). These materials are distinctive among reported iSF compounds because they exist in the unexplored regime of close spatial proximity but weak electronic coupling between the singlet exciton and triplet pair states. Using transient absorption spectroscopy to investigate photophysics in these molecules, we find that homoconjugated dimers display desirable excited-state dynamics, with significantly reduced recombination rates as compared to conjugated dimers with similar singlet fission rates. In addition, unlike conjugated dimers, the time constants for singlet fission are relatively insensitive to the interplanar angle between chromophores, since rotation about σ bonds negligibly affects the orbital overlap within the π-bonding network. In the nonconjugated dimer, where the iSF occurs with a time constant >10 ns, comparable to the fluorescence lifetime, we used electron spin resonance spectroscopy to unequivocally establish the formation of triplet–triplet multiexcitons and uncoupled triplet excitons through singlet fission. Together, these studies enable us to articulate the role of the conjugation motif in iSF.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [3];  [4];  [5];  [1];  [1];  [1];  [1];  [6];  [1]; ORCiD logo [6];  [1];  [5];  [3]; ORCiD logo [7]; ORCiD logo [1]
  1. Columbia Univ., New York, NY (United States). Department of Chemistry
  2. University of New South Wales, Sydney (Australia). School of Photovoltaic and Renewable Energy Engineering; University of Cambridge (United Kingdom). Cavendish Laboratory
  3. University of New South Wales, Sydney (Australia). ARC Centre of Excellence in Exciton Science, School of Physics
  4. Cornell Univ., Ithaca, NY (United States). Department of Chemistry and Chemical Biology; Cambridge University (United Kingdom). Jesus College
  5. Cornell Univ., Ithaca, NY (United States). Department of Chemistry and Chemical Biology
  6. Princeton Univ., NJ (United States). Department of Chemistry
  7. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1413948
Report Number(s):
BNL-114743-2017-JA
Journal ID: ISSN 0002-7863; KC0403020; TRN: US1800601
Grant/Contract Number:  
SC0012704; SC0015429
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 36; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Singlet Fission; Homoconjugated Dimers; Non-Conjugated; Organic Electronics; Pentacene Dimers; Electron Spin Resonance; Center for Functional Nanomaterials

Citation Formats

Kumarasamy, Elango, Sanders, Samuel N., Tayebjee, Murad J. Y., Asadpoordarvish, Amir, Hele, Timothy J. H., Fuemmeler, Eric G., Pun, Andrew B., Yablon, Lauren M., Low, Jonathan Z., Paley, Daniel W., Dean, Jacob C., Choi, Bonnie, Scholes, Gregory D., Steigerwald, Michael L., Ananth, Nandini, McCamey, Dane R., Sfeir, Matthew Y., and Campos, Luis M. Tuning Singlet Fission in π-Bridge-π Chromophores. United States: N. p., 2017. Web. doi:10.1021/jacs.7b05204.
Kumarasamy, Elango, Sanders, Samuel N., Tayebjee, Murad J. Y., Asadpoordarvish, Amir, Hele, Timothy J. H., Fuemmeler, Eric G., Pun, Andrew B., Yablon, Lauren M., Low, Jonathan Z., Paley, Daniel W., Dean, Jacob C., Choi, Bonnie, Scholes, Gregory D., Steigerwald, Michael L., Ananth, Nandini, McCamey, Dane R., Sfeir, Matthew Y., & Campos, Luis M. Tuning Singlet Fission in π-Bridge-π Chromophores. United States. doi:10.1021/jacs.7b05204.
Kumarasamy, Elango, Sanders, Samuel N., Tayebjee, Murad J. Y., Asadpoordarvish, Amir, Hele, Timothy J. H., Fuemmeler, Eric G., Pun, Andrew B., Yablon, Lauren M., Low, Jonathan Z., Paley, Daniel W., Dean, Jacob C., Choi, Bonnie, Scholes, Gregory D., Steigerwald, Michael L., Ananth, Nandini, McCamey, Dane R., Sfeir, Matthew Y., and Campos, Luis M. Fri . "Tuning Singlet Fission in π-Bridge-π Chromophores". United States. doi:10.1021/jacs.7b05204. https://www.osti.gov/servlets/purl/1413948.
@article{osti_1413948,
title = {Tuning Singlet Fission in π-Bridge-π Chromophores},
author = {Kumarasamy, Elango and Sanders, Samuel N. and Tayebjee, Murad J. Y. and Asadpoordarvish, Amir and Hele, Timothy J. H. and Fuemmeler, Eric G. and Pun, Andrew B. and Yablon, Lauren M. and Low, Jonathan Z. and Paley, Daniel W. and Dean, Jacob C. and Choi, Bonnie and Scholes, Gregory D. and Steigerwald, Michael L. and Ananth, Nandini and McCamey, Dane R. and Sfeir, Matthew Y. and Campos, Luis M.},
abstractNote = {For this study, we have designed a series of pentacene dimers separated by homoconjugated or nonconjugated bridges that exhibit fast and efficient intramolecular singlet exciton fission (iSF). These materials are distinctive among reported iSF compounds because they exist in the unexplored regime of close spatial proximity but weak electronic coupling between the singlet exciton and triplet pair states. Using transient absorption spectroscopy to investigate photophysics in these molecules, we find that homoconjugated dimers display desirable excited-state dynamics, with significantly reduced recombination rates as compared to conjugated dimers with similar singlet fission rates. In addition, unlike conjugated dimers, the time constants for singlet fission are relatively insensitive to the interplanar angle between chromophores, since rotation about σ bonds negligibly affects the orbital overlap within the π-bonding network. In the nonconjugated dimer, where the iSF occurs with a time constant >10 ns, comparable to the fluorescence lifetime, we used electron spin resonance spectroscopy to unequivocally establish the formation of triplet–triplet multiexcitons and uncoupled triplet excitons through singlet fission. Together, these studies enable us to articulate the role of the conjugation motif in iSF.},
doi = {10.1021/jacs.7b05204},
journal = {Journal of the American Chemical Society},
number = 36,
volume = 139,
place = {United States},
year = {2017},
month = {8}
}

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Cited by: 30 works
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Figures / Tables:

Figure 1. Figure 1.: The pentacene-bridge-pentacene model showing the comparison between different bridging units. In the bottom representations, the pentacenes are omitted to highlight the nature of the bridging units.

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Works referencing / citing this record:

Conformational Planarization versus Singlet Fission: Distinct Excited-State Dynamics of Cyclooctatetraene-Fused Acene Dimers
journal, March 2018

  • Yamakado, Takuya; Takahashi, Shota; Watanabe, Kazuya
  • Angewandte Chemie International Edition, Vol. 57, Issue 19
  • DOI: 10.1002/anie.201802185

Azaarene Dimers
journal, March 2019

  • Hahn, Sebastian; Butscher, Julian; An, Qingzhi
  • Chemistry – A European Journal, Vol. 25, Issue 30
  • DOI: 10.1002/chem.201901139

Using sulfur bridge oxidation to control electronic coupling and photochemistry in covalent anthracene dimers
journal, January 2019

  • Cruz, Chad D.; Yuan, Jennifer; Climent, Clàudia
  • Chemical Science, Vol. 10, Issue 32
  • DOI: 10.1039/c8sc05598j

Davydov splitting and singlet fission in excitonically coupled pentacene dimers
journal, January 2019

  • Basel, Bettina Sabine; Hetzer, Constantin; Zirzlmeier, Johannes
  • Chemical Science, Vol. 10, Issue 13
  • DOI: 10.1039/c9sc00384c

A molecular movie of ultrafast singlet fission
journal, September 2019

  • Schnedermann, Christoph; Alvertis, Antonios M.; Wende, Torsten
  • Nature Communications, Vol. 10, Issue 1
  • DOI: 10.1038/s41467-019-12220-7

Substituent effects on energetics and crystal morphology modulate singlet fission in 9,10-bis(phenylethynyl)anthracenes
journal, July 2019

  • Bae, Youn Jue; Christensen, Joseph A.; Kang, Gyeongwon
  • The Journal of Chemical Physics, Vol. 151, Issue 4
  • DOI: 10.1063/1.5110411

Conformational Planarization versus Singlet Fission: Distinct Excited-State Dynamics of Cyclooctatetraene-Fused Acene Dimers
journal, March 2018

  • Yamakado, Takuya; Takahashi, Shota; Watanabe, Kazuya
  • Angewandte Chemie International Edition, Vol. 57, Issue 19
  • DOI: 10.1002/anie.201802185

Azaarene Dimers
journal, March 2019

  • Hahn, Sebastian; Butscher, Julian; An, Qingzhi
  • Chemistry – A European Journal, Vol. 25, Issue 30
  • DOI: 10.1002/chem.201901139

A molecular movie of ultrafast singlet fission
journal, September 2019

  • Schnedermann, Christoph; Alvertis, Antonios M.; Wende, Torsten
  • Nature Communications, Vol. 10, Issue 1
  • DOI: 10.1038/s41467-019-12220-7

Using sulfur bridge oxidation to control electronic coupling and photochemistry in covalent anthracene dimers
journal, January 2019

  • Cruz, Chad D.; Yuan, Jennifer; Climent, Clàudia
  • Chemical Science, Vol. 10, Issue 32
  • DOI: 10.1039/c8sc05598j

Davydov splitting and singlet fission in excitonically coupled pentacene dimers
journal, January 2019

  • Basel, Bettina Sabine; Hetzer, Constantin; Zirzlmeier, Johannes
  • Chemical Science, Vol. 10, Issue 13
  • DOI: 10.1039/c9sc00384c

Substituent effects on energetics and crystal morphology modulate singlet fission in 9,10-bis(phenylethynyl)anthracenes
journal, July 2019

  • Bae, Youn Jue; Christensen, Joseph A.; Kang, Gyeongwon
  • The Journal of Chemical Physics, Vol. 151, Issue 4
  • DOI: 10.1063/1.5110411

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