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Title: Solvent-Controlled Branching of Localized versus Delocalized Singlet Exciton States and Equilibration with Charge Transfer in a Structurally Well-Defined Tetracene Dimer

Abstract

A detailed photophysical picture is elaborated for a structurally well-defined and symmetrical bis-tetracene dimer in solution. The molecule was designed for interrogation of the initial photophysical steps (S 1 → 1TT) in intramolecular singlet fission (SF). (Triisopropylsilyl)acetylene substituents on the dimer TIPS-BT1 as well as a monomer model TIPS-Tc enable a comparison of photophysical properties, including transient absorption dynamics, as solvent polarity is varied. In nonpolar toluene solutions, TIPS-BT1 decays via radiative and nonradiative pathways to the ground state with no evidence for dynamics related to the initial stages of SF. This contrasts with the behavior of the previously reported unsubstituted dimer BT1 and is likely a consequence of energetic perturbations to the singlet excited-state manifold of TIPS-BT1 by the (trialkylsilyl)acetylene substituents. In polar benzonitrile, two key findings emerge. First, photoexcited TIPS-BT1 shows a bifurcation into both arm-localized (S 1-loc) and dimer-delocalized (S 1-dim) singlet exciton states. The S 1-loc decays to the ground state, and weak temperature dependence of its emissive signatures suggests that once it is formed, it is isolated from S 1-dim. Emissive signatures of the S 1-dim state, on the other hand, are strongly temperature-dependent, and transient absorption dynamics show that S1-dim equilibrates with an intramolecularmore » charge-transfer state in 50 ps at room temperature. This equilibrium decays to the ground state with little evidence for formation of long-lived triplets nor 1TT. These detailed studies spectrally characterize many of the key states in intramolecular SF in this class of dimers but highlight the need to tune electronic coupling and energetics for the S 1 → 1TT photoreaction.« less

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
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  1. Univ. of Colorado, Boulder, CO (United States). Dept. of Chemistry and Biochemistry
  2. 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); National Science Foundation (NSF)
OSTI Identifier:
1410974
Report Number(s):
NREL/JA-5900-70332
Journal ID: ISSN 1089-5639; TRN: US1800168
Grant/Contract Number:  
AC36-08GO28308; AC02-05CH11231; FG02-07ER15890; CHE-1665375
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 121; Journal Issue: 48; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; SINGLET FISSION; DIMERS; PHOTOPHYSICS

Citation Formats

Cook, Jasper D., Carey, Thomas J., Arias, Dylan H., Johnson, Justin C., and Damrauer, Niels H. Solvent-Controlled Branching of Localized versus Delocalized Singlet Exciton States and Equilibration with Charge Transfer in a Structurally Well-Defined Tetracene Dimer. United States: N. p., 2017. Web. doi:10.1021/acs.jpca.7b09458.
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Cook, Jasper D., Carey, Thomas J., Arias, Dylan H., Johnson, Justin C., & Damrauer, Niels H. Solvent-Controlled Branching of Localized versus Delocalized Singlet Exciton States and Equilibration with Charge Transfer in a Structurally Well-Defined Tetracene Dimer. United States. doi:10.1021/acs.jpca.7b09458.
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Cook, Jasper D., Carey, Thomas J., Arias, Dylan H., Johnson, Justin C., and Damrauer, Niels H. Sat . "Solvent-Controlled Branching of Localized versus Delocalized Singlet Exciton States and Equilibration with Charge Transfer in a Structurally Well-Defined Tetracene Dimer". United States. doi:10.1021/acs.jpca.7b09458. https://www.osti.gov/servlets/purl/1410974.
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@article{osti_1410974,
title = {Solvent-Controlled Branching of Localized versus Delocalized Singlet Exciton States and Equilibration with Charge Transfer in a Structurally Well-Defined Tetracene Dimer},
author = {Cook, Jasper D. and Carey, Thomas J. and Arias, Dylan H. and Johnson, Justin C. and Damrauer, Niels H.},
abstractNote = {A detailed photophysical picture is elaborated for a structurally well-defined and symmetrical bis-tetracene dimer in solution. The molecule was designed for interrogation of the initial photophysical steps (S1 → 1TT) in intramolecular singlet fission (SF). (Triisopropylsilyl)acetylene substituents on the dimer TIPS-BT1 as well as a monomer model TIPS-Tc enable a comparison of photophysical properties, including transient absorption dynamics, as solvent polarity is varied. In nonpolar toluene solutions, TIPS-BT1 decays via radiative and nonradiative pathways to the ground state with no evidence for dynamics related to the initial stages of SF. This contrasts with the behavior of the previously reported unsubstituted dimer BT1 and is likely a consequence of energetic perturbations to the singlet excited-state manifold of TIPS-BT1 by the (trialkylsilyl)acetylene substituents. In polar benzonitrile, two key findings emerge. First, photoexcited TIPS-BT1 shows a bifurcation into both arm-localized (S1-loc) and dimer-delocalized (S1-dim) singlet exciton states. The S1-loc decays to the ground state, and weak temperature dependence of its emissive signatures suggests that once it is formed, it is isolated from S1-dim. Emissive signatures of the S1-dim state, on the other hand, are strongly temperature-dependent, and transient absorption dynamics show that S1-dim equilibrates with an intramolecular charge-transfer state in 50 ps at room temperature. This equilibrium decays to the ground state with little evidence for formation of long-lived triplets nor 1TT. These detailed studies spectrally characterize many of the key states in intramolecular SF in this class of dimers but highlight the need to tune electronic coupling and energetics for the S1 → 1TT photoreaction.},
doi = {10.1021/acs.jpca.7b09458},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 48,
volume = 121,
place = {United States},
year = {2017},
month = {11}
}
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DOI:  10.1021/acs.jpca.7b09458
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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

Enhancing the intermolecular singlet fission efficiency by controlling the self-assembly of amphipathic tetracene derivatives in aqueous solution
journal, January 2019

  • Tang, Zhaofeng; Zhou, Sainan; Wang, Xiangyang
  • Journal of Materials Chemistry C, Vol. 7, Issue 36
  • DOI: 10.1039/c9tc04070f
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