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 »
- Authors:
-
- Univ. of Colorado, Boulder, CO (United States). Dept. of Chemistry and Biochemistry
- 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.
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
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.
@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}
}
Web of Science
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
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
Singlet Fission
journal, November 2010
- Smith, Millicent B.; Michl, Josef
- Chemical Reviews, Vol. 110, Issue 11
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
Bimolecular radiationless transitions in crystalline tetracene
journal, September 1968
- Swenberg, C. E.; Stacy, W. T.
- Chemical Physics Letters, Vol. 2, Issue 5
Fission of singlet excitons into pairs of triplet excitons in tetracene crystals
journal, June 1969
- Merrifield, R. E.; Avakian, P.; Groff, R. P.
- Chemical Physics Letters, Vol. 3, Issue 6
Recent Advances in Singlet Fission
journal, April 2013
- Smith, Millicent B.; Michl, Josef
- Annual Review of Physical Chemistry, Vol. 64, Issue 1
Evidence for exciton fission and fusion in a covalently linked tetracene dimer
journal, April 2006
- Müller, Astrid M.; Avlasevich, Yuri S.; Müllen, Klaus
- Chemical Physics Letters, Vol. 421, Issue 4-6
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
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
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
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
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
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
Symmetry-Directed Control of Electronic Coupling for Singlet Fission in Covalent Bis–Acene Dimers
journal, October 2015
- Damrauer, Niels H.; Snyder, Jamie L.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 22
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
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
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
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
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
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
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
Design of Small Intramolecular Singlet Fission Chromophores: An Azaborine Candidate and General Small Size Effects
journal, March 2016
- Zeng, Tao; Goel, Prateek
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 7
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
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
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
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
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
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
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
Quintet multiexciton dynamics in singlet fission
journal, October 2016
- Tayebjee, Murad J. Y.; Sanders, Samuel N.; Kumarasamy, Elango
- Nature Physics, Vol. 13, Issue 2
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
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
Singlet Fission in Polypentacene
journal, September 2016
- Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B.
- Chem, Vol. 1, Issue 3
A Covalently Linked Tetracene Trimer: Synthesis and Singlet Exciton Fission Property
journal, January 2017
- Liu, Heyuan; Wang, Rui; Shen, Li
- Organic Letters, Vol. 19, Issue 3
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
Two ideas on energy transfer phenomena: Ion-pair effects involving the OH stretching mode, and sensitization of photovoltaic cells
journal, January 1979
- Dexter, D. L.
- Journal of Luminescence, Vol. 18-19
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
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
Enhanced Triplet Formation in Polycrystalline Tetracene Films by Femtosecond Optical-Pulse Shaping
journal, December 2010
- Grumstrup, Erik M.; Johnson, Justin C.; Damrauer, Niels H.
- Physical Review Letters, Vol. 105, Issue 25
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
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
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
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
Solvatochromic Dyes as Solvent Polarity Indicators
journal, December 1994
- Reichardt, Christian
- Chemical Reviews, Vol. 94, Issue 8
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
On the (uninteresting) dependence of the absorption and emission transition moments of coumarin 153 on solvent
journal, January 1998
- Lewis, J. E.; Maroncelli, M.
- Chemical Physics Letters, Vol. 282, Issue 2
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
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
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
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
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
Photoinduced Electron Transfer in Solution: Exciplex and Radical Ion Pair Formation Free Enthalpies and their Solvent Dependence
journal, January 1982
- Weller, Albert
- Zeitschrift für Physikalische Chemie, Vol. 133, Issue 1
Ligand Structure, Conformational Dynamics, and Excited-State Electron Delocalization for Control of Photoinduced Electron Transfer Rates in Synthetic Donor-Bridge-Acceptor Systems
journal, April 2008
- Meylemans, Heather A.; Lei, Chi-Fong; Damrauer, Niels H.
- Inorganic Chemistry, Vol. 47, Issue 10
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
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
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
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, Vol. 130, Issue 19
Heavy-atom effects on intramolecular singlet fission in a conjugated polymer
journal, July 2019
- Musser, Andrew J.; Al-Hashimi, Mohammed; Heeney, Martin
- The Journal of Chemical Physics, Vol. 151, Issue 4
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
Weakly coupled triplet pair states probed by quantum beating in delayed fluorescence in tetracene crystals
journal, October 2019
- Wang, Zhiwei; Zhang, Chunfeng; Wang, Rui
- The Journal of Chemical Physics, Vol. 151, Issue 13
Striking the right balance of intermolecular coupling for high-efficiency singlet fission
journal, January 2018
- Pensack, Ryan D.; Tilley, Andrew J.; Grieco, Christopher
- Chemical Science, Vol. 9, Issue 29
Singlet exciton fission in a linear tetracene tetramer
journal, January 2018
- Liu, Heyuan; Wang, Zhiwei; Wang, Xuemin
- Journal of Materials Chemistry C, Vol. 6, Issue 13
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
Striking the right balance of intermolecular coupling for high-efficiency singlet fission
journal, January 2018
- Pensack, Ryan D.; Tilley, Andrew J.; Grieco, Christopher
- Chemical Science, Vol. 9, Issue 29