Revealing the Singlet Fission Mechanism for a Silane-Bridged Thienotetracene Dimer

Liang Chun Lin; Ryan D. Dill; Karl J. Thorley; Sean R. Parkin; John E. Anthony; Justin C. Johnson; Niels H. Damrauer

doi:10.1021/acs.jpca.4c01463

Revealing the Singlet Fission Mechanism for a Silane-Bridged Thienotetracene Dimer

Liang Chun Lin
, Ryan D. Dill
, Karl J. Thorley
, Sean R. Parkin
, John E. Anthony
, Justin C. Johnson
, Niels H. Damrauer

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

Tetraceno[2,3-b]thiophene is regarded as a strong candidate for singlet fission-based solar cell applications due to its mixed characteristics of tetracene and pentacene that balance exothermicity and triplet energy. An electronically weakly coupled tetraceno[2,3-b]thiophene dimer (Et₂Si(TIPSTT)₂) with a single silicon atom bridge has been synthesized, providing a new platform to investigate the singlet fission mechanism involving the two acene chromophores. We study the excited state dynamics of Et₂Si(TIPSTT)₂ by monitoring the evolution of multiexciton coupled triplet states, ¹TT to ⁵TT to ³TT to T₁ + S₀, upon photoexcitation with transient absorption, temperature-dependent transient absorption, and transient/pulsed electron paramagnetic resonance spectroscopies. We find that the photoexcited singlet lifetime is 107 ps, with 90% evolving to form the TT state, and the complicated evolution between the multiexciton states is unraveled, which can be an important reference for future efforts toward tetraceno[2,3-b]thiophene-based singlet fission solar cells.

Original language	English
Pages (from-to)	3982-3992
Number of pages	11
Journal	Journal of Physical Chemistry A
Volume	128
Issue number	20
DOIs	https://doi.org/10.1021/acs.jpca.4c01463
State	Published - May 23 2024

Bibliographical note

Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.

Funding

Synthesis work was funded by the United States Department of Energy, Office of Basic Energy Sciences (ERW7404), and through Cooperative Agreement No. 1849213 with the National Science Foundation. Optical spectroscopy and analysis were supported by the National Science Foundation (CHE-2102713). Time-resolved electron paramagnetic resonance spectroscopy and analysis were funded by the Solar Photochemistry Program of the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences, and Geosciences. This work was authored in part by Alliance for Sustainable Energy, Limited Liability Company, the manager and operator of the National Renewable Energy Laboratory under contract no. DE-AC36-08GO28308. The views expressed in the article do not necessarily represent the views of the Department of Energy or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes.

Funders	Funder number
Chemical Sciences, Geosciences, and Biosciences Division
U.S. Department of Energy
National Science Foundation Arctic Social Science Program	1849213, 2102713
National Renewable Energy Laboratory	DE-AC36-08GO28308
DOE Basic Energy Sciences	ERW7404

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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title = "Revealing the Singlet Fission Mechanism for a Silane-Bridged Thienotetracene Dimer",

abstract = "Tetraceno[2,3-b]thiophene is regarded as a strong candidate for singlet fission-based solar cell applications due to its mixed characteristics of tetracene and pentacene that balance exothermicity and triplet energy. An electronically weakly coupled tetraceno[2,3-b]thiophene dimer (Et2Si(TIPSTT)2) with a single silicon atom bridge has been synthesized, providing a new platform to investigate the singlet fission mechanism involving the two acene chromophores. We study the excited state dynamics of Et2Si(TIPSTT)2 by monitoring the evolution of multiexciton coupled triplet states, 1TT to 5TT to 3TT to T1 + S0, upon photoexcitation with transient absorption, temperature-dependent transient absorption, and transient/pulsed electron paramagnetic resonance spectroscopies. We find that the photoexcited singlet lifetime is 107 ps, with 90\% evolving to form the TT state, and the complicated evolution between the multiexciton states is unraveled, which can be an important reference for future efforts toward tetraceno[2,3-b]thiophene-based singlet fission solar cells.",

author = "Lin, \{Liang Chun\} and Dill, \{Ryan D.\} and Thorley, \{Karl J.\} and Parkin, \{Sean R.\} and Anthony, \{John E.\} and Johnson, \{Justin C.\} and Damrauer, \{Niels H.\}",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society.",

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doi = "10.1021/acs.jpca.4c01463",

language = "English",

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AU - Lin, Liang Chun

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AU - Thorley, Karl J.

AU - Parkin, Sean R.

AU - Anthony, John E.

AU - Johnson, Justin C.

AU - Damrauer, Niels H.

PY - 2024/5/23

Y1 - 2024/5/23

N2 - Tetraceno[2,3-b]thiophene is regarded as a strong candidate for singlet fission-based solar cell applications due to its mixed characteristics of tetracene and pentacene that balance exothermicity and triplet energy. An electronically weakly coupled tetraceno[2,3-b]thiophene dimer (Et2Si(TIPSTT)2) with a single silicon atom bridge has been synthesized, providing a new platform to investigate the singlet fission mechanism involving the two acene chromophores. We study the excited state dynamics of Et2Si(TIPSTT)2 by monitoring the evolution of multiexciton coupled triplet states, 1TT to 5TT to 3TT to T1 + S0, upon photoexcitation with transient absorption, temperature-dependent transient absorption, and transient/pulsed electron paramagnetic resonance spectroscopies. We find that the photoexcited singlet lifetime is 107 ps, with 90% evolving to form the TT state, and the complicated evolution between the multiexciton states is unraveled, which can be an important reference for future efforts toward tetraceno[2,3-b]thiophene-based singlet fission solar cells.

AB - Tetraceno[2,3-b]thiophene is regarded as a strong candidate for singlet fission-based solar cell applications due to its mixed characteristics of tetracene and pentacene that balance exothermicity and triplet energy. An electronically weakly coupled tetraceno[2,3-b]thiophene dimer (Et2Si(TIPSTT)2) with a single silicon atom bridge has been synthesized, providing a new platform to investigate the singlet fission mechanism involving the two acene chromophores. We study the excited state dynamics of Et2Si(TIPSTT)2 by monitoring the evolution of multiexciton coupled triplet states, 1TT to 5TT to 3TT to T1 + S0, upon photoexcitation with transient absorption, temperature-dependent transient absorption, and transient/pulsed electron paramagnetic resonance spectroscopies. We find that the photoexcited singlet lifetime is 107 ps, with 90% evolving to form the TT state, and the complicated evolution between the multiexciton states is unraveled, which can be an important reference for future efforts toward tetraceno[2,3-b]thiophene-based singlet fission solar cells.

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Revealing the Singlet Fission Mechanism for a Silane-Bridged Thienotetracene Dimer

Abstract

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