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

doi:10.1021/acs.jpca.7b09458

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

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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 »

Authors:

Cook, Jasper D. ^[1] ; Carey, Thomas J. ^[1] ; ; ;

Univ. of Colorado, Boulder, CO (United States). Dept. of Chemistry and Biochemistry
National Renewable Energy Lab. (NREL), Golden, CO (United States)

Publication Date:: 2017-11-04

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

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

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)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; SINGLET FISSION; DIMERS; PHOTOPHYSICS

OSTI Identifier:: 1410974


                    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.,  
        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.. 2017.  
        "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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10.1021/acs.jpca.7b09458
https://doi.org/10.1021/acs.jpca.7b09458

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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

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