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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 (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 atmore » 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.« 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 Laboratory (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); 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. https://doi.org/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. https://doi.org/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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https://doi.org/10.1021/acs.jpca.7b09458
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Works referenced in this record:

Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers
journal, October 2006

  • Hanna, M. C.; Nozik, A. J.
  • Journal of Applied Physics, Vol. 100, Issue 7
  • DOI: 10.1063/1.2356795

Third Generation Photovoltaics based on Multiple Exciton Generation in Quantum Confined Semiconductors
journal, October 2012

  • Beard, Matthew C.; Luther, Joseph M.; Semonin, Octavi E.
  • Accounts of Chemical Research, Vol. 46, Issue 6
  • DOI: 10.1021/ar3001958

Singlet Fission
journal, November 2010

  • Smith, Millicent B.; Michl, Josef
  • Chemical Reviews, Vol. 110, Issue 11
  • DOI: 10.1021/cr1002613

Laser Generation of Excitons and Fluorescence in Anthracene Crystals
journal, January 1965

  • Singh, S.; Jones, W. J.; Siebrand, W.
  • The Journal of Chemical Physics, Vol. 42, Issue 1
  • DOI: 10.1063/1.1695695

Bimolecular radiationless transitions in crystalline tetracene
journal, September 1968

Fission of singlet excitons into pairs of triplet excitons in tetracene crystals
journal, June 1969

Recent Advances in Singlet Fission
journal, April 2013

Evidence for exciton fission and fusion in a covalently linked tetracene dimer
journal, April 2006

Exciton Fission and Fusion in Bis(tetracene) Molecules with Different Covalent Linker Structures
journal, November 2007

  • Müller, Astrid M.; Avlasevich, Yuri S.; Schoeller, Wolfgang W.
  • Journal of the American Chemical Society, Vol. 129, Issue 46, p. 14240-14250
  • DOI: 10.1021/ja073173y

Toward Designed Singlet Fission: Solution Photophysics of Two Indirectly Coupled Covalent Dimers of 1,3-Diphenylisobenzofuran
journal, November 2012

  • Johnson, Justin C.; Akdag, Akin; Zamadar, Matibur
  • The Journal of Physical Chemistry B, Vol. 117, Issue 16
  • DOI: 10.1021/jp310979q

Tunable Electronic Coupling and Driving Force in Structurally Well-Defined Tetracene Dimers for Molecular Singlet Fission: A Computational Exploration Using Density Functional Theory
journal, September 2013

  • Vallett, Paul J.; Snyder, Jamie L.; Damrauer, Niels H.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 42
  • DOI: 10.1021/jp407426q

Anti -[2.2](1,4)pentacenophane: A Covalently Coupled Pentacene Dimer
journal, September 2013

  • Bula, Rafael; Fingerle, Michael; Ruff, Adrian
  • Angewandte Chemie International Edition, Vol. 52, Issue 44
  • DOI: 10.1002/anie.201303649

Covalent Dimers of 1,3-Diphenylisobenzofuran for Singlet Fission: Synthesis and Electrochemistry
journal, December 2014

  • Akdag, Akin; Wahab, Abdul; Beran, Pavel
  • The Journal of Organic Chemistry, Vol. 80, Issue 1
  • DOI: 10.1021/jo502004r

Exploring Non-Condon Effects in a Covalent Tetracene Dimer: How Important Are Vibrations in Determining the Electronic Coupling for Singlet Fission?
journal, December 2014

  • Alguire, Ethan C.; Subotnik, Joseph E.; Damrauer, Niels H.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 2
  • DOI: 10.1021/jp510777c

Symmetry-Directed Control of Electronic Coupling for Singlet Fission in Covalent Bis–Acene Dimers
journal, October 2015

Tuneable Singlet Exciton Fission and Triplet-Triplet Annihilation in an Orthogonal Pentacene Dimer
journal, August 2015

  • Lukman, Steven; Musser, Andrew J.; Chen, Kai
  • Advanced Functional Materials, Vol. 25, Issue 34
  • DOI: 10.1002/adfm.201501537

Singlet fission in pentacene dimers
journal, April 2015

  • Zirzlmeier, Johannes; Lehnherr, Dan; Coto, Pedro B.
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 17
  • DOI: 10.1073/pnas.1422436112

Quantitative Intramolecular Singlet Fission in Bipentacenes
journal, July 2015

  • Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B.
  • Journal of the American Chemical Society, Vol. 137, Issue 28
  • DOI: 10.1021/jacs.5b04986

Synthesis and photophysical properties of a “face-to-face” stacked tetracene dimer
journal, January 2015

  • Liu, Heyuan; Nichols, Valerie M.; Shen, Li
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 9
  • DOI: 10.1039/C4CP05444J

Solution-Phase Singlet Fission in a Structurally Well-Defined Norbornyl-Bridged Tetracene Dimer
journal, June 2016

  • Cook, Jasper D.; Carey, Thomas J.; Damrauer, Niels H.
  • The Journal of Physical Chemistry A, Vol. 120, Issue 26
  • DOI: 10.1021/acs.jpca.6b04367

Excitation Localization/Delocalization Isomerism in a Strongly Coupled Covalent Dimer of 1,3-Diphenylisobenzofuran
journal, May 2016

  • Schrauben, Joel N.; Akdag, Akin; Wen, Jin
  • The Journal of Physical Chemistry A, Vol. 120, Issue 20
  • DOI: 10.1021/acs.jpca.6b00826

Singlet Fission in a Covalently Linked Cofacial Alkynyltetracene Dimer
journal, January 2016

  • Korovina, Nadezhda V.; Das, Saptaparna; Nett, Zachary
  • Journal of the American Chemical Society, Vol. 138, Issue 2
  • DOI: 10.1021/jacs.5b10550

Design of Small Intramolecular Singlet Fission Chromophores: An Azaborine Candidate and General Small Size Effects
journal, March 2016

Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering
journal, December 2016

  • Lukman, Steven; Chen, Kai; Hodgkiss, Justin M.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13622

Enabling singlet fission by controlling intramolecular charge transfer in π-stacked covalent terrylenediimide dimers
journal, August 2016

  • Margulies, Eric A.; Miller, Claire E.; Wu, Yilei
  • Nature Chemistry, Vol. 8, Issue 12
  • DOI: 10.1038/nchem.2589

Intramolecular Singlet Fission in Oligoacene Heterodimers
journal, February 2016

  • Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B.
  • Angewandte Chemie International Edition, Vol. 55, Issue 10
  • DOI: 10.1002/anie.201510632

Exciton Correlations in Intramolecular Singlet Fission
journal, June 2016

  • Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B.
  • Journal of the American Chemical Society, Vol. 138, Issue 23
  • DOI: 10.1021/jacs.6b00657

Long-Lived Triplet Excited States of Bent-Shaped Pentacene Dimers by Intramolecular Singlet Fission
journal, March 2016

  • Sakuma, Takao; Sakai, Hayato; Araki, Yasuyuki
  • The Journal of Physical Chemistry A, Vol. 120, Issue 11
  • DOI: 10.1021/acs.jpca.6b00988

Synthesis of Geometrically Well-Defined Covalent Acene Dimers for Mechanistic Exploration of Singlet Fission
journal, April 2017

  • Carey, Thomas J.; Snyder, Jamie L.; Miller, Ethan G.
  • The Journal of Organic Chemistry, Vol. 82, Issue 9
  • DOI: 10.1021/acs.joc.7b00602

Unified model for singlet fission within a non-conjugated covalent pentacene dimer
journal, May 2017

  • Basel, Bettina S.; Zirzlmeier, Johannes; Hetzer, Constantin
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15171

Quintet multiexciton dynamics in singlet fission
journal, October 2016

  • Tayebjee, Murad J. Y.; Sanders, Samuel N.; Kumarasamy, Elango
  • Nature Physics, Vol. 13, Issue 2
  • DOI: 10.1038/nphys3909

Tuning Singlet Fission in π-Bridge-π Chromophores
journal, September 2017

  • Kumarasamy, Elango; Sanders, Samuel N.; Tayebjee, Murad J. Y.
  • Journal of the American Chemical Society, Vol. 139, Issue 36
  • DOI: 10.1021/jacs.7b05204

Photophysical characterization and time-resolved spectroscopy of a anthradithiophene dimer: exploring the role of conformation in singlet fission
journal, January 2017

  • Dean, Jacob C.; Zhang, Ruomeng; Hallani, Rawad K.
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 34
  • DOI: 10.1039/C7CP03774K

Singlet Fission in Polypentacene
journal, September 2016

A Covalently Linked Tetracene Trimer: Synthesis and Singlet Exciton Fission Property
journal, January 2017

Photocurrent Enhanced by Singlet Fission in a Dye-Sensitized Solar Cell
journal, January 2015

  • Schrauben, Joel N.; Zhao, Yixin; Mercado, Candy
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 4
  • DOI: 10.1021/am506329v

Microscopic theory of singlet exciton fission. II. Application to pentacene dimers and the role of superexchange
journal, March 2013

  • Berkelbach, Timothy C.; Hybertsen, Mark S.; Reichman, David R.
  • The Journal of Chemical Physics, Vol. 138, Issue 11
  • DOI: 10.1063/1.4794427

Maximizing Singlet Fission in Organic Dimers: Theoretical Investigation of Triplet Yield in the Regime of Localized Excitation and Fast Coherent Electron Transfer †
journal, November 2010

  • Greyson, Eric C.; Vura-Weis, Josh; Michl, Josef
  • The Journal of Physical Chemistry B, Vol. 114, Issue 45
  • DOI: 10.1021/jp907392q

Enhanced Triplet Formation in Polycrystalline Tetracene Films by Femtosecond Optical-Pulse Shaping
journal, December 2010

An Efficient Synthetic Strategy for Naphthalene Annellation of Norbornenylogous Systems
journal, January 1986

  • Paddon-Row, Michael N.; Patney, Harish K.
  • Synthesis, Vol. 1986, Issue 04
  • DOI: 10.1055/s-1986-31603

Through-space and through-bond effects on exciton interactions in rigidly linked dinaphthyl molecules
journal, May 1993

  • Scholes, Gregory D.; Ghiggino, Kenneth P.; Oliver, Anna M.
  • Journal of the American Chemical Society, Vol. 115, Issue 10
  • DOI: 10.1021/ja00063a061

The Role of Chromophore Coupling in Singlet Fission
journal, January 2013

  • Johnson, Justin C.; Nozik, Arthur J.; Michl, Josef
  • Accounts of Chemical Research, Vol. 46, Issue 6
  • DOI: 10.1021/ar300193r

The Spectral Signatures of Frenkel Polarons in H- and J-Aggregates
journal, March 2010

  • Spano, Frank C.
  • Accounts of Chemical Research, Vol. 43, Issue 3
  • DOI: 10.1021/ar900233v

Solvatochromic Dyes as Solvent Polarity Indicators
journal, December 1994

Nature of ground and electronic excited states of higher acenes
journal, August 2016

  • Yang, Yang; Davidson, Ernest R.; Yang, Weitao
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 35
  • DOI: 10.1073/pnas.1606021113

On the (uninteresting) dependence of the absorption and emission transition moments of coumarin 153 on solvent
journal, January 1998

Identification of a triplet pair intermediate in singlet exciton fission in solution
journal, June 2015

  • Stern, Hannah L.; Musser, Andrew J.; Gelinas, Simon
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 25
  • DOI: 10.1073/pnas.1503471112

Photophysical properties of tetracene derivatives in solution. 2. Halogenated tetracene derivatives
journal, May 1991

  • Burgdorff, C.; Ehrhardt, S.; Loehmannsroeben, H. G.
  • The Journal of Physical Chemistry, Vol. 95, Issue 11
  • DOI: 10.1021/j100164a016

Polyene 21Ag and 11Bu states and the photochemistry of previtamin D3
journal, October 1991

  • Dauben, William G.; Disanayaka, Bimsara; Funhoff, Dirk J. H.
  • Journal of the American Chemical Society, Vol. 113, Issue 22
  • DOI: 10.1021/ja00022a025

Laser dye stability. Part 5: Effect of chemical substituents of bicyclic dyes upon photodegradation parameters
journal, July 1978

  • Fletcher, Aaron N.; Bliss, Dan E.
  • Applied Physics, Vol. 16, Issue 3
  • DOI: 10.1007/BF00885124

Molecular structure and the temperature-dependent radiative rates in Twisted Intramolecular Charge-Transfer and exciplex systems
journal, March 1991

  • Van der Auweraer, Mark; Grabowski, Zbigniew R.; Rettig, Wolfgang
  • The Journal of Physical Chemistry, Vol. 95, Issue 5
  • DOI: 10.1021/j100158a033

Solvent-dependent intramolecular charge transfer delocalization/localization in multibranched push-pull chromophores
journal, July 2015

  • Li, Yang; Zhou, Meng; Niu, Yingli
  • The Journal of Chemical Physics, Vol. 143, Issue 3
  • DOI: 10.1063/1.4926998

Photoinduced symmetry-breaking intramolecular charge transfer in a quadrupolar pyridinium derivative
journal, January 2014

  • Carlotti, Benedetta; Benassi, Enrico; Spalletti, Anna
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 27
  • DOI: 10.1039/C4CP00631C

Charge Instability in Quadrupolar Chromophores:  Symmetry Breaking and Solvatochromism
journal, December 2006

  • Terenziani, Francesca; Painelli, Anna; Katan, Claudine
  • Journal of the American Chemical Society, Vol. 128, Issue 49
  • DOI: 10.1021/ja064521j
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