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Title: Unified model for singlet fission within a non-conjugated covalent pentacene dimer

When molecular dimers, crystalline films or molecular aggregates absorb a photon to produce a singlet exciton, spin-allowed singlet fission may produce two triplet excitons that can be used to generate two electron–hole pairs, leading to a predicted B50% enhancement in maximum solar cell performance. The singlet fission mechanism is still not well understood. Here we report on the use of time-resolved optical and electron paramagnetic resonance spectroscopy to probe singlet fission in a pentacene dimer linked by a non-conjugated spacer. We observe the key intermediates in the singlet fission process, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons. In conclusion, using these combined data, we develop a single kinetic model that describes the data over seven temporal orders of magnitude both at room and cryogenic temperatures.
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [2] ;  [1] ;  [1] ;  [2] ;  [2] ;  [3] ;  [1] ;  [1] ;  [1] ;  [4] ;  [2] ;  [1]
  1. Friedrich-Alexander-Univ. Erlangen-Nurnberg (FAU), Erlangen (Germany)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Rigaku Europe, Sevenoaks (United Kingdom)
  4. Friedrich-Alexander-Univ. Erlangen-Nurnberg (FAU), Erlangen (Germany); Univ. of Alberta, Edmonton, AB (Canada)
Publication Date:
Grant/Contract Number:
FG02-99ER14999
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Excited states; Spectrophotometry
OSTI Identifier:
1389775

Basel, Bettina S., Zirzlmeier, Johannes, Hetzer, Constantin, Phelan, Brian T., Krzyaniak, Matthew D., Reddy, S. Rajagopala, Coto, Pedro B., Horwitz, Noah E., Young, Ryan M., White, Fraser J., Hampel, Frank, Clark, Timothy, Thoss, Michael, Tykwinski, Rik R., Wasielewski, Michael R., and Guldi, Dirk M.. Unified model for singlet fission within a non-conjugated covalent pentacene dimer. United States: N. p., Web. doi:10.1038/ncomms15171.
Basel, Bettina S., Zirzlmeier, Johannes, Hetzer, Constantin, Phelan, Brian T., Krzyaniak, Matthew D., Reddy, S. Rajagopala, Coto, Pedro B., Horwitz, Noah E., Young, Ryan M., White, Fraser J., Hampel, Frank, Clark, Timothy, Thoss, Michael, Tykwinski, Rik R., Wasielewski, Michael R., & Guldi, Dirk M.. Unified model for singlet fission within a non-conjugated covalent pentacene dimer. United States. doi:10.1038/ncomms15171.
Basel, Bettina S., Zirzlmeier, Johannes, Hetzer, Constantin, Phelan, Brian T., Krzyaniak, Matthew D., Reddy, S. Rajagopala, Coto, Pedro B., Horwitz, Noah E., Young, Ryan M., White, Fraser J., Hampel, Frank, Clark, Timothy, Thoss, Michael, Tykwinski, Rik R., Wasielewski, Michael R., and Guldi, Dirk M.. 2017. "Unified model for singlet fission within a non-conjugated covalent pentacene dimer". United States. doi:10.1038/ncomms15171. https://www.osti.gov/servlets/purl/1389775.
@article{osti_1389775,
title = {Unified model for singlet fission within a non-conjugated covalent pentacene dimer},
author = {Basel, Bettina S. and Zirzlmeier, Johannes and Hetzer, Constantin and Phelan, Brian T. and Krzyaniak, Matthew D. and Reddy, S. Rajagopala and Coto, Pedro B. and Horwitz, Noah E. and Young, Ryan M. and White, Fraser J. and Hampel, Frank and Clark, Timothy and Thoss, Michael and Tykwinski, Rik R. and Wasielewski, Michael R. and Guldi, Dirk M.},
abstractNote = {When molecular dimers, crystalline films or molecular aggregates absorb a photon to produce a singlet exciton, spin-allowed singlet fission may produce two triplet excitons that can be used to generate two electron–hole pairs, leading to a predicted B50% enhancement in maximum solar cell performance. The singlet fission mechanism is still not well understood. Here we report on the use of time-resolved optical and electron paramagnetic resonance spectroscopy to probe singlet fission in a pentacene dimer linked by a non-conjugated spacer. We observe the key intermediates in the singlet fission process, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons. In conclusion, using these combined data, we develop a single kinetic model that describes the data over seven temporal orders of magnitude both at room and cryogenic temperatures.},
doi = {10.1038/ncomms15171},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {2017},
month = {5}
}

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