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Title: Spin Dynamics of Quintet and Triplet States Resulting from Singlet Fission in Oriented Terrylenediimide and Quaterrylenediimide Films

Abstract

Singlet fission in organic semiconductors provides an important opportunity to study high-spin states in electronically coupled chromophores. Photoexcitation of oriented, crystalline films of N,N-bis(pentadec-8-yl)terrylene-3,4:11,12-bis(dicarboximide) (TDI) and N,N-bis (pentadec-8-yl)quaterrylene-3,4:13,14-bis(dicarboximide) (QDI) result in the formation of the correlated triplet pair quintet state, 5(T1T1) and its subsequent dissociation into two triplet (T-1) excitons. Time-resolved electron paramagnetic resonance (TREPR) spectroscopy and X-ray crystallography are used to show that the orientation dependence of 5(T1T1) spin dynamics is retained as it dissociates into two T1 excitons, while such information is lost in a randomly oriented sample. In addition, the spin dynamics depend on how the molecules are oriented relative to the external applied magnetic field. Dissociation of 5(T1T1) to form two T1 excitons is more efficient in TDI and leads to a longer T-1 lifetime than in QDI, making TDI a more viable candidate for photovoltaic applications. Since QDI readily forms a highly oriented film, and the lifetime of its 5(T1T1) state is longer than that of TDI, it may be a good candidate for quantum information science applications that require the generation of a quantum- entangled, four-spin state.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Northwestern Univ., Evanston, IL (United States)
  2. Saitama Univ. (Japan)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1635107
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 124; Journal Issue: 18; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Bae, Youn Jue, Zhao, Xingang, Kryzaniak, Matthew D., Nagashima, Hiroki, Strzalka, Joseph, Zhang, Qingteng, and Wasielewski, Michael R. Spin Dynamics of Quintet and Triplet States Resulting from Singlet Fission in Oriented Terrylenediimide and Quaterrylenediimide Films. United States: N. p., 2020. Web. doi:10.1021/acs.jpcc.0c03189.
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Bae, Youn Jue, Zhao, Xingang, Kryzaniak, Matthew D., Nagashima, Hiroki, Strzalka, Joseph, Zhang, Qingteng, & Wasielewski, Michael R. Spin Dynamics of Quintet and Triplet States Resulting from Singlet Fission in Oriented Terrylenediimide and Quaterrylenediimide Films. United States. https://doi.org/10.1021/acs.jpcc.0c03189
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Bae, Youn Jue, Zhao, Xingang, Kryzaniak, Matthew D., Nagashima, Hiroki, Strzalka, Joseph, Zhang, Qingteng, and Wasielewski, Michael R. Tue . "Spin Dynamics of Quintet and Triplet States Resulting from Singlet Fission in Oriented Terrylenediimide and Quaterrylenediimide Films". United States. https://doi.org/10.1021/acs.jpcc.0c03189. https://www.osti.gov/servlets/purl/1635107.
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@article{osti_1635107,
title = {Spin Dynamics of Quintet and Triplet States Resulting from Singlet Fission in Oriented Terrylenediimide and Quaterrylenediimide Films},
author = {Bae, Youn Jue and Zhao, Xingang and Kryzaniak, Matthew D. and Nagashima, Hiroki and Strzalka, Joseph and Zhang, Qingteng and Wasielewski, Michael R.},
abstractNote = {Singlet fission in organic semiconductors provides an important opportunity to study high-spin states in electronically coupled chromophores. Photoexcitation of oriented, crystalline films of N,N-bis(pentadec-8-yl)terrylene-3,4:11,12-bis(dicarboximide) (TDI) and N,N-bis (pentadec-8-yl)quaterrylene-3,4:13,14-bis(dicarboximide) (QDI) result in the formation of the correlated triplet pair quintet state, 5(T1T1) and its subsequent dissociation into two triplet (T-1) excitons. Time-resolved electron paramagnetic resonance (TREPR) spectroscopy and X-ray crystallography are used to show that the orientation dependence of 5(T1T1) spin dynamics is retained as it dissociates into two T1 excitons, while such information is lost in a randomly oriented sample. In addition, the spin dynamics depend on how the molecules are oriented relative to the external applied magnetic field. Dissociation of 5(T1T1) to form two T1 excitons is more efficient in TDI and leads to a longer T-1 lifetime than in QDI, making TDI a more viable candidate for photovoltaic applications. Since QDI readily forms a highly oriented film, and the lifetime of its 5(T1T1) state is longer than that of TDI, it may be a good candidate for quantum information science applications that require the generation of a quantum- entangled, four-spin state.},
doi = {10.1021/acs.jpcc.0c03189},
journal = {Journal of Physical Chemistry. C},
number = 18,
volume = 124,
place = {United States},
year = {Tue Apr 14 00:00:00 EDT 2020},
month = {Tue Apr 14 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/acs.jpcc.0c03189
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Works referenced in this record:

The role of spin in the kinetic control of recombination in organic photovoltaics
journal, August 2013

  • Rao, Akshay; Chow, Philip C. Y.; Gélinas, Simon
  • Nature, Vol. 500, Issue 7463
  • DOI: 10.1038/nature12339

Sensitization of silicon by singlet exciton fission in tetracene
journal, July 2019

Energy harvesting of non-emissive triplet excitons in tetracene by emissive PbS nanocrystals
journal, October 2014

  • Thompson, Nicholas J.; Wilson, Mark W. B.; Congreve, Daniel N.
  • Nature Materials, Vol. 13, Issue 11
  • DOI: 10.1038/nmat4097

Resonant energy transfer of triplet excitons from pentacene to PbSe nanocrystals
journal, October 2014

  • Tabachnyk, Maxim; Ehrler, Bruno; Gélinas, Simon
  • Nature Materials, Vol. 13, Issue 11
  • DOI: 10.1038/nmat4093

Strongly exchange-coupled triplet pairs in an organic semiconductor
journal, October 2016

  • Weiss, Leah R.; Bayliss, Sam L.; Kraffert, Felix
  • Nature Physics, Vol. 13, Issue 2
  • DOI: 10.1038/nphys3908

Singlet Fission in Covalent Terrylenediimide Dimers: Probing the Nature of the Multiexciton State Using Femtosecond Mid-Infrared Spectroscopy
journal, June 2018

  • Chen, Michelle; Bae, Youn Jue; Mauck, Catherine M.
  • Journal of the American Chemical Society, Vol. 140, Issue 29
  • DOI: 10.1021/jacs.8b04830

Fluctuating exchange interactions enable quintet multiexciton formation in singlet fission
journal, October 2019

  • Collins, Miles I.; McCamey, Dane R.; Tayebjee, Murad J. Y.
  • The Journal of Chemical Physics, Vol. 151, Issue 16
  • DOI: 10.1063/1.5115816

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

Quintet-triplet mixing determines the fate of the multiexciton state produced by singlet fission in a terrylenediimide dimer at room temperature
journal, April 2019

  • Chen, Michelle; Krzyaniak, Matthew D.; Nelson, Jordan N.
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 17
  • DOI: 10.1073/pnas.1820932116

Singlet Fission in 9,10-Bis(phenylethynyl)anthracene Thin Films
journal, October 2018

  • Bae, Youn Jue; Kang, Gyeongwon; Malliakas, Christos D.
  • Journal of the American Chemical Society, Vol. 140, Issue 45
  • DOI: 10.1021/jacs.8b07498

Substituent effects on energetics and crystal morphology modulate singlet fission in 9,10-bis(phenylethynyl)anthracenes
journal, July 2019

  • Bae, Youn Jue; Christensen, Joseph A.; Kang, Gyeongwon
  • The Journal of Chemical Physics, Vol. 151, Issue 4
  • DOI: 10.1063/1.5110411

Recent Advances in Singlet Fission
journal, April 2013

Site-selective measurement of coupled spin pairs in an organic semiconductor
journal, May 2018

  • Bayliss, S. L.; Weiss, L. R.; Mitioglu, A.
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 20
  • DOI: 10.1073/pnas.1718868115

Quantum Beats in Crystalline Tetracene Delayed Fluorescence Due to Triplet Pair Coherences Produced by Direct Singlet Fission
journal, May 2012

  • Burdett, Jonathan J.; Bardeen, Christopher J.
  • Journal of the American Chemical Society, Vol. 134, Issue 20
  • DOI: 10.1021/ja301683w

The entangled triplet pair state in acene and heteroacene materials
journal, July 2017

  • Yong, Chaw Keong; Musser, Andrew J.; Bayliss, Sam L.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15953

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

Varying the Interpentacene Electronic Coupling to Tune Singlet Fission
journal, March 2019

  • Papadopoulos, Ilias; Zirzlmeier, Johannes; Hetzer, Constantin
  • Journal of the American Chemical Society, Vol. 141, Issue 15
  • DOI: 10.1021/jacs.8b09510

Identifying triplet pathways in dilute pentacene films
journal, October 2018

  • Lubert-Perquel, Daphné; Salvadori, Enrico; Dyson, Matthew
  • Nature Communications, Vol. 9, Issue 1
  • DOI: 10.1038/s41467-018-06330-x

Tuning Spin Dynamics in Crystalline Tetracene
journal, March 2019

  • Bayliss, Sam L.; Kraffert, Felix; Wang, Rui
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 8
  • DOI: 10.1021/acs.jpclett.9b00356

Exploiting Excited-State Aromaticity To Design Highly Stable Singlet Fission Materials
journal, August 2019

  • Fallon, Kealan J.; Budden, Peter; Salvadori, Enrico
  • Journal of the American Chemical Society, Vol. 141, Issue 35
  • DOI: 10.1021/jacs.9b06346

Rylene and Related Diimides for Organic Electronics
journal, December 2010

  • Zhan, Xiaowei; Facchetti, Antonio; Barlow, Stephen
  • Advanced Materials, Vol. 23, Issue 2, p. 268-284
  • DOI: 10.1002/adma.201001402

Geometry and Electronic Coupling in Perylenediimide Stacks: Mapping Structure−Charge Transport Relationships
journal, February 2010

  • Vura-Weis, Josh; Ratner, Mark A.; Wasielewski, Michael R.
  • Journal of the American Chemical Society, Vol. 132, Issue 6
  • DOI: 10.1021/ja907761e

Singlet Fission Involves an Interplay between Energetic Driving Force and Electronic Coupling in Perylenediimide Films
journal, January 2018

  • Le, Aaron K.; Bender, Jon A.; Arias, Dylan H.
  • Journal of the American Chemical Society, Vol. 140, Issue 2
  • DOI: 10.1021/jacs.7b11888

Singlet Exciton Fission in Polycrystalline Thin Films of a Slip-Stacked Perylenediimide
journal, September 2013

  • Eaton, Samuel W.; Shoer, Leah E.; Karlen, Steven D.
  • Journal of the American Chemical Society, Vol. 135, Issue 39
  • DOI: 10.1021/ja4053174

Direct Observation of a Charge-Transfer State Preceding High-Yield Singlet Fission in Terrylenediimide Thin Films
journal, December 2016

  • Margulies, Eric A.; Logsdon, Jenna L.; Miller, Claire E.
  • Journal of the American Chemical Society, Vol. 139, Issue 2
  • DOI: 10.1021/jacs.6b07721

On the possibility of singlet fission in crystalline quaterrylene
journal, May 2018

  • Wang, Xiaopeng; Liu, Xingyu; Cook, Cameron
  • The Journal of Chemical Physics, Vol. 148, Issue 18
  • DOI: 10.1063/1.5027553

Singlet Fission in Quaterrylenediimide Thin Films
journal, January 2020

  • Chen, Michelle; Powers-Riggs, Natalia E.; Coleman, Adam F.
  • The Journal of Physical Chemistry C, Vol. 124, Issue 5
  • DOI: 10.1021/acs.jpcc.9b10397

Pronounced Supramolecular Order in Discotic Donor–Acceptor Mixtures
journal, January 2006

  • Pisula, Wojciech; Kastler, Marcel; Wasserfallen, Daniel
  • Angewandte Chemie International Edition, Vol. 45, Issue 5
  • DOI: 10.1002/anie.200500669

Synthesis and Self-Organization of Core-Extended Perylene Tetracarboxdiimides with Branched Alkyl Substituents
journal, August 2006

  • Nolde, Fabian; Pisula, Wojciech; Müller, Sibylle
  • Chemistry of Materials, Vol. 18, Issue 16
  • DOI: 10.1021/cm060742c

OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009

  • Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
  • Journal of Applied Crystallography, Vol. 42, Issue 2
  • DOI: 10.1107/S0021889808042726

The dedicated high-resolution grazing-incidence X-ray scattering beamline 8-ID-E at the Advanced Photon Source
journal, June 2012

  • Jiang, Zhang; Li, Xuefa; Strzalka, Joseph
  • Journal of Synchrotron Radiation, Vol. 19, Issue 4
  • DOI: 10.1107/S0909049512022017

Photovoltaic Blend Microstructure for High Efficiency Post-Fullerene Solar Cells. To Tilt or Not To Tilt?
journal, August 2019

  • Wang, Gang; Swick, Steven M.; Matta, Micaela
  • Journal of the American Chemical Society, Vol. 141, Issue 34
  • DOI: 10.1021/jacs.9b03770

Impact of Polymer Side Chain Modification on OPV Morphology and Performance
journal, October 2018

Quantitative Determination of Organic Semiconductor Microstructure from the Molecular to Device Scale
journal, June 2012

  • Rivnay, Jonathan; Mannsfeld, Stefan C. B.; Miller, Chad E.
  • Chemical Reviews, Vol. 112, Issue 10
  • DOI: 10.1021/cr3001109

EasySpin, a comprehensive software package for spectral simulation and analysis in EPR
journal, January 2006

Exergonic Intramolecular Singlet Fission of an Adamantane-Linked Tetracene Dyad via Twin Quintet Multiexcitons
journal, July 2019

  • Matsui, Yasunori; Kawaoka, Shuhei; Nagashima, Hiroki
  • The Journal of Physical Chemistry C, Vol. 123, Issue 31
  • DOI: 10.1021/acs.jpcc.9b04503

Electron spin polarization generated by transport of singlet and quintet multiexcitons to spin-correlated triplet pairs during singlet fissions
journal, January 2020

  • Matsuda, Saki; Oyama, Shinya; Kobori, Yasuhiro
  • Chemical Science, Vol. 11, Issue 11
  • DOI: 10.1039/C9SC04949E

Effects of Crystal Morphology on Singlet Exciton Fission in Diketopyrrolopyrrole Thin Films
journal, February 2016

  • Hartnett, Patrick E.; Margulies, Eric A.; Mauck, Catherine M.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 7
  • DOI: 10.1021/acs.jpcb.5b10565

Molecular Packing and Singlet Fission: The Parent and Three Fluorinated 1,3-Diphenylisobenzofurans
journal, March 2019

  • Buchanan, Eric A.; Kaleta, Jiří; Wen, Jin
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 8
  • DOI: 10.1021/acs.jpclett.8b03875

Molecular Aggregate Photophysics beyond the Kasha Model: Novel Design Principles for Organic Materials
journal, January 2017

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

Competition between Singlet Fission and Spin‐Orbit‐Induced Intersystem Crossing in Anthanthrene and Anthanthrone Derivatives
journal, June 2019

  • Jue Bae, Youn; Krzyaniak, Matthew D.; Majewski, Marek B.
  • ChemPlusChem, Vol. 84, Issue 9
  • DOI: 10.1002/cplu.201900410

The photoexcited triplet state and photosynthesis
journal, June 1978

What Can Be Learned from Magnetic Field Effects on Singlet Fission: Role of Exchange Interaction in Excited Triplet Pairs
journal, November 2015

  • Wakasa, Masanobu; Kaise, Mana; Yago, Tomoaki
  • The Journal of Physical Chemistry C, Vol. 119, Issue 46
  • DOI: 10.1021/acs.jpcc.5b10176

Magnetic Field Effects on Triplet Pair Generated by Singlet Fission in an Organic Crystal: Application of Radical Pair Model to Triplet Pair
journal, December 2016

  • Yago, Tomoaki; Ishikawa, Kei; Katoh, Ryuzi
  • The Journal of Physical Chemistry C, Vol. 120, Issue 49
  • DOI: 10.1021/acs.jpcc.6b09570

Principles and applications of EPR spectroscopy in the chemical sciences
journal, January 2018

  • Roessler, Maxie M.; Salvadori, Enrico
  • Chemical Society Reviews, Vol. 47, Issue 8
  • DOI: 10.1039/C6CS00565A

Intersystem Crossing Mediated by Photoinduced Intramolecular Charge Transfer:  Julolidine−Anthracene Molecules with Perpendicular π Systems
journal, May 2008

  • Dance, Zachary E. X.; Mickley, Sarah M.; Wilson, Thea M.
  • The Journal of Physical Chemistry A, Vol. 112, Issue 18
  • DOI: 10.1021/jp800561g

Time-Resolved EPR Studies of Charge Recombination and Triplet-State Formation within Donor−Bridge−Acceptor Molecules Having Wire-Like Oligofluorene Bridges
journal, May 2010

  • Miura, Tomoaki; Carmieli, Raanan; Wasielewski, Michael R.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 18
  • DOI: 10.1021/jp101523n

Singlet-Fission-Born Quintet State: Sublevel Selections and Trapping by Multiexciton Thermodynamics
journal, September 2018

  • Nagashima, Hiroki; Kawaoka, Shuhei; Akimoto, Seiji
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 19
  • DOI: 10.1021/acs.jpclett.8b02396
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