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Title: Spatial separation of triplet excitons drives endothermic singlet fission

Abstract

Molecules that undergo singlet fission, converting singlet excitons into pairs of triplet excitons, have potential as photovoltaic materials. The possible advantages of endothermic singlet fission (enhanced use of photon energy and larger triplet energies for coupling with common absorbers) motivated us to assess the role of exciton delocalization in the activation of this process. Here we report the synthesis of a series of linear perylene oligomers that undergo endothermic singlet fission and have endothermicities in the range 5-10 kBT at room temperature in solution. We study these compounds using transient spectroscopy and modelling to unravel the singlet and triplet dynamics. We show that the minimal number of coupled chromophores needed to undergo endothermic singlet fission is three, which provides sufficient statistical space for triplet excitons to separate and avoid annihilation - and a subsequent fast return to the singlet state. Our data additionally suggest that torsional motion of chromophores about the molecular axis following triplet-pair separation contributes to the increase in entropy, thus lengthening the triplet lifetime in longer oligomers.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Renewable Energy Laboratory (NREL), Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1605078
Report Number(s):
NREL/JA-5900-72986
Journal ID: ISSN 1755-4330
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Name: Nature Chemistry; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; singlet fission; triplet; excitons; dimers; oligomers; spectroscopy; perylene; organic photovoltaic materials

Citation Formats

Korovina, Nadezhda, Chang, Christopher H., and Johnson, Justin C. Spatial separation of triplet excitons drives endothermic singlet fission. United States: N. p., 2020. Web. doi:10.1038/s41557-020-0422-7.
Korovina, Nadezhda, Chang, Christopher H., & Johnson, Justin C. Spatial separation of triplet excitons drives endothermic singlet fission. United States. doi:10.1038/s41557-020-0422-7.
Korovina, Nadezhda, Chang, Christopher H., and Johnson, Justin C. Mon . "Spatial separation of triplet excitons drives endothermic singlet fission". United States. doi:10.1038/s41557-020-0422-7.
@article{osti_1605078,
title = {Spatial separation of triplet excitons drives endothermic singlet fission},
author = {Korovina, Nadezhda and Chang, Christopher H. and Johnson, Justin C.},
abstractNote = {Molecules that undergo singlet fission, converting singlet excitons into pairs of triplet excitons, have potential as photovoltaic materials. The possible advantages of endothermic singlet fission (enhanced use of photon energy and larger triplet energies for coupling with common absorbers) motivated us to assess the role of exciton delocalization in the activation of this process. Here we report the synthesis of a series of linear perylene oligomers that undergo endothermic singlet fission and have endothermicities in the range 5-10 kBT at room temperature in solution. We study these compounds using transient spectroscopy and modelling to unravel the singlet and triplet dynamics. We show that the minimal number of coupled chromophores needed to undergo endothermic singlet fission is three, which provides sufficient statistical space for triplet excitons to separate and avoid annihilation - and a subsequent fast return to the singlet state. Our data additionally suggest that torsional motion of chromophores about the molecular axis following triplet-pair separation contributes to the increase in entropy, thus lengthening the triplet lifetime in longer oligomers.},
doi = {10.1038/s41557-020-0422-7},
journal = {Nature Chemistry},
number = ,
volume = ,
place = {United States},
year = {2020},
month = {3}
}

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