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Title: Singlet fission in a hexacene dimer: energetics dictate dynamics

Abstract

Singlet fission (SF) is an exciton multiplication process with the potential to raise the efficiency limit of single junction solar cells from 33% to up to 45%. Most chromophores generally undergo SF as solid-state crystals. However, when such molecules are covalently coupled, the dimers can be used as model systems to study fundamental photophysical dynamics where a singlet exciton splits into two triplet excitons within individual molecules. Here we report the synthesis and photophysical characterization of singlet fission of a hexacene dimer. Comparing the hexacene dimer to analogous tetracene and pentacene dimers reveals that excess exoergicity slows down singlet fission, similar to what is observed in molecular crystals. Conversely, the lower triplet energy of hexacene results in an increase in the rate of triplet pair recombination, following the energy gap law for radiationless transitions. These results point to design rules for singlet fission chromophores: the energy gap between singlet and triplet pair should be minimal, and the gap between triplet pair and ground state should be large.

Authors:
 [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Columbia Univ., New York, NY (United States). Dept. of Chemistry
  2. City Univ. of New York (CUNY), NY (United States). Photonics Initiative; City Univ. of New York (CUNY), NY (United States). Graduate Center. Dept. of Physics
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; US Department of the Navy, Office of Naval Research (ONR); National Science Foundation (NSF)
OSTI Identifier:
1816620
Grant/Contract Number:  
SC0012704; N00014-15-1-2532; DGE 11-44155
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 11; Journal Issue: 4; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Sanders, Samuel N., Kumarasamy, Elango, Fallon, Kealan J., Sfeir, Matthew Y., and Campos, Luis M. Singlet fission in a hexacene dimer: energetics dictate dynamics. United States: N. p., 2019. Web. doi:10.1039/c9sc05066c.
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Sanders, Samuel N., Kumarasamy, Elango, Fallon, Kealan J., Sfeir, Matthew Y., & Campos, Luis M. Singlet fission in a hexacene dimer: energetics dictate dynamics. United States. https://doi.org/10.1039/c9sc05066c
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Sanders, Samuel N., Kumarasamy, Elango, Fallon, Kealan J., Sfeir, Matthew Y., and Campos, Luis M. Mon . "Singlet fission in a hexacene dimer: energetics dictate dynamics". United States. https://doi.org/10.1039/c9sc05066c. https://www.osti.gov/servlets/purl/1816620.
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@article{osti_1816620,
title = {Singlet fission in a hexacene dimer: energetics dictate dynamics},
author = {Sanders, Samuel N. and Kumarasamy, Elango and Fallon, Kealan J. and Sfeir, Matthew Y. and Campos, Luis M.},
abstractNote = {Singlet fission (SF) is an exciton multiplication process with the potential to raise the efficiency limit of single junction solar cells from 33% to up to 45%. Most chromophores generally undergo SF as solid-state crystals. However, when such molecules are covalently coupled, the dimers can be used as model systems to study fundamental photophysical dynamics where a singlet exciton splits into two triplet excitons within individual molecules. Here we report the synthesis and photophysical characterization of singlet fission of a hexacene dimer. Comparing the hexacene dimer to analogous tetracene and pentacene dimers reveals that excess exoergicity slows down singlet fission, similar to what is observed in molecular crystals. Conversely, the lower triplet energy of hexacene results in an increase in the rate of triplet pair recombination, following the energy gap law for radiationless transitions. These results point to design rules for singlet fission chromophores: the energy gap between singlet and triplet pair should be minimal, and the gap between triplet pair and ground state should be large.},
doi = {10.1039/c9sc05066c},
journal = {Chemical Science},
number = 4,
volume = 11,
place = {United States},
year = {Mon Dec 09 00:00:00 EST 2019},
month = {Mon Dec 09 00:00:00 EST 2019}
}
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Works referenced in this record:

Femtosecond Raman Microscopy Reveals Structural Dynamics Leading to Triplet Separation in Rubrene Singlet Fission
journal, November 2017

  • Bera, Kajari; Douglas, Christopher J.; Frontiera, Renee R.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 23
  • DOI: 10.1021/acs.jpclett.7b02769

Multiphonon Relaxation Slows Singlet Fission in Crystalline Hexacene
journal, July 2014

  • Busby, Erik; Berkelbach, Timothy C.; Kumar, Bharat
  • Journal of the American Chemical Society, Vol. 136, Issue 30
  • DOI: 10.1021/ja503980c

A Road Map to Stable, Soluble, Easily Crystallized Pentacene Derivatives
journal, January 2002

  • Anthony, John E.; Eaton, David L.; Parkin, Sean R.
  • Organic Letters, Vol. 4, Issue 1
  • DOI: 10.1021/ol0167356

Ultra-fast intramolecular singlet fission to persistent multiexcitons by molecular design
journal, August 2019

  • Pun, Andrew B.; Asadpoordarvish, Amir; Kumarasamy, Elango
  • Nature Chemistry, Vol. 11, Issue 9
  • DOI: 10.1038/s41557-019-0297-7

Low band gap polycyclic hydrocarbons: from closed-shell near infrared dyes and semiconductors to open-shell radicals
journal, January 2012

  • Sun, Zhe; Ye, Qun; Chi, Chunyan
  • Chemical Society Reviews, Vol. 41, Issue 23
  • DOI: 10.1039/c2cs35211g

Phosphorescent heavy-metal complexes for bioimaging
journal, January 2011

  • Zhao, Qiang; Huang, Chunhui; Li, Fuyou
  • Chemical Society Reviews, Vol. 40, Issue 5
  • DOI: 10.1039/c0cs00114g

Recent Advances in Singlet Fission
journal, April 2013

Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy
journal, October 2015

  • Bakulin, Artem A.; Morgan, Sarah E.; Kehoe, Tom B.
  • Nature Chemistry, Vol. 8, Issue 1
  • DOI: 10.1038/nchem.2371

Linker-Dependent Singlet Fission in Tetracene Dimers
journal, July 2018

  • Korovina, Nadezhda V.; Joy, Jimmy; Feng, Xintian
  • Journal of the American Chemical Society, Vol. 140, Issue 32
  • DOI: 10.1021/jacs.8b04401

Solution-based intramolecular singlet fission in cross-conjugated pentacene dimers
journal, January 2016

  • Zirzlmeier, Johannes; Casillas, Rubén; Reddy, S. Rajagopala
  • Nanoscale, Vol. 8, Issue 19
  • DOI: 10.1039/C6NR02493A

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

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

Long-Lived Correlated Triplet Pairs in a π-Stacked Crystalline Pentacene Derivative
journal, February 2018

  • Folie, Brendan D.; Haber, Jonah B.; Refaely-Abramson, Sivan
  • Journal of the American Chemical Society, Vol. 140, Issue 6
  • DOI: 10.1021/jacs.7b12662

Controlling Singlet Fission by Molecular Contortion
journal, July 2019

  • Conrad-Burton, Felisa S.; Liu, Taifeng; Geyer, Florian
  • Journal of the American Chemical Society, Vol. 141, Issue 33
  • DOI: 10.1021/jacs.9b05357

Singlet fission in pentacene through multi-exciton quantum states
journal, June 2010

  • Zimmerman, Paul M.; Zhang, Zhiyong; Musgrave, Charles B.
  • Nature Chemistry, Vol. 2, Issue 8
  • DOI: 10.1038/nchem.694

Persistent Multiexcitons from Polymers with Pendent Pentacenes
journal, April 2019

  • Yablon, Lauren M.; Sanders, Samuel N.; Li, Hua
  • Journal of the American Chemical Society, Vol. 141, Issue 24
  • DOI: 10.1021/jacs.9b02241

Properties of Poly- and Oligopentacenes Synthesized from Modular Building Blocks
journal, February 2016

Functionalized Higher Acenes:  Hexacene and Heptacene
journal, June 2005

  • Payne, Marcia M.; Parkin, Sean R.; Anthony, John E.
  • Journal of the American Chemical Society, Vol. 127, Issue 22
  • DOI: 10.1021/ja051798v

Imaging and Photodynamic Therapy: Mechanisms, Monitoring, and Optimization
journal, May 2010

  • Celli, Jonathan P.; Spring, Bryan Q.; Rizvi, Imran
  • Chemical Reviews, Vol. 110, Issue 5
  • DOI: 10.1021/cr900300p

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

Application of the energy gap law to nonradiative, excited-state decay
journal, March 1983

  • Caspar, Jonathan V.; Meyer, Thomas J.
  • The Journal of Physical Chemistry, Vol. 87, Issue 6
  • DOI: 10.1021/j100229a010

Phosphorescent chemosensors based on heavy-metal complexes
journal, January 2010

  • Zhao, Qiang; Li, Fuyou; Huang, Chunhui
  • Chemical Society Reviews, Vol. 39, Issue 8
  • DOI: 10.1039/b915340c

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

Diagrammatic Exciton Basis Theory of the Photophysics of Pentacene Dimers
journal, September 2017

Vibronic exciton theory of singlet fission. III. How vibronic coupling and thermodynamics promote rapid triplet generation in pentacene crystals
journal, June 2018

  • Tempelaar, Roel; Reichman, David R.
  • The Journal of Chemical Physics, Vol. 148, Issue 24
  • DOI: 10.1063/1.5031778

Excessive Exoergicity Reduces Singlet Exciton Fission Efficiency of Heteroacenes in Solutions
journal, May 2016

  • Zhang, You-Dan; Wu, Yishi; Xu, Yanqing
  • Journal of the American Chemical Society, Vol. 138, Issue 21
  • DOI: 10.1021/jacs.6b03829

The energy gap law for radiationless transitions in large molecules
journal, February 1970

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

Singlet Exciton Fission Photovoltaics
journal, April 2013

  • Lee, Jiye; Jadhav, Priya; Reusswig, Philip D.
  • Accounts of Chemical Research, Vol. 46, Issue 6
  • DOI: 10.1021/ar300288e

Multiexciton Dynamics Depending on Intramolecular Orientations in Pentacene Dimers: Recombination and Dissociation of Correlated Triplet Pairs
journal, May 2018

  • Sakai, Hayato; Inaya, Ryutaro; Nagashima, Hiroki
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 12
  • DOI: 10.1021/acs.jpclett.8b01184

The Energy Gap Law for Triplet States in Pt-Containing Conjugated Polymers and Monomers
journal, September 2001

  • Wilson, Joanne S.; Chawdhury, Nazia; Al-Mandhary, Muna R. A.
  • Journal of the American Chemical Society, Vol. 123, Issue 38
  • DOI: 10.1021/ja010986s

Vibronic fingerprint of singlet fission in hexacene
journal, August 2019

  • Deng, Gang-Hua; Wei, Qianshun; Han, Jian
  • The Journal of Chemical Physics, Vol. 151, Issue 5
  • DOI: 10.1063/1.5110263

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

Oligoacenes:  Theoretical Prediction of Open-Shell Singlet Diradical Ground States
journal, June 2004

  • Bendikov, Michael; Duong, Hieu M.; Starkey, Kyle
  • Journal of the American Chemical Society, Vol. 126, Issue 24
  • DOI: 10.1021/ja048919w

A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers
journal, May 2016

Understanding the Bound Triplet-Pair State in Singlet Fission
journal, August 2019

Vibronically coherent ultrafast triplet-pair formation and subsequent thermally activated dissociation control efficient endothermic singlet fission
journal, September 2017

  • Stern, Hannah L.; Cheminal, Alexandre; Yost, Shane R.
  • Nature Chemistry, Vol. 9, Issue 12
  • DOI: 10.1038/nchem.2856

Electronic spectra of hexacene in solution (ground state. Triplet state. Dication and dianion)
journal, March 1982

Distinct properties of the triplet pair state from singlet fission
journal, July 2017

  • Trinh, M. Tuan; Pinkard, Andrew; Pun, Andrew B.
  • Science Advances, Vol. 3, Issue 7
  • DOI: 10.1126/sciadv.1700241

Photon upconversion based on sensitized triplet–triplet annihilation
journal, November 2010

  • Singh-Rachford, Tanya N.; Castellano, Felix N.
  • Coordination Chemistry Reviews, Vol. 254, Issue 21-22
  • DOI: 10.1016/j.ccr.2010.01.003

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

Photoredox catalysis using infrared light via triplet fusion upconversion
journal, January 2019

Singlet Fission
journal, November 2010

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

Triplet Harvesting from Intramolecular Singlet Fission in Polytetracene
journal, September 2017

  • Pun, Andrew B.; Sanders, Samuel N.; Kumarasamy, Elango
  • Advanced Materials, Vol. 29, Issue 41
  • DOI: 10.1002/adma.201701416

Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene
journal, December 2016

  • Monahan, Nicholas R.; Sun, Dezheng; Tamura, Hiroyuki
  • Nature Chemistry, Vol. 9, Issue 4
  • DOI: 10.1038/nchem.2665

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

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

The Dynamics of Singlet Fission in Crystalline Tetracene and Covalent Analogs
journal, January 2013

  • Burdett, Jonathan J.; Bardeen, Christopher J.
  • Accounts of Chemical Research, Vol. 46, Issue 6
  • DOI: 10.1021/ar300191w

A design strategy for intramolecular singlet fission mediated by charge-transfer states in donor–acceptor organic materials
journal, January 2015

  • Busby, Erik; Xia, Jianlong; Wu, Qin
  • Nature Materials, Vol. 14, Issue 4
  • DOI: 10.1038/nmat4175

Annihilator dimers enhance triplet fusion upconversion
journal, January 2019

  • Pun, Andrew B.; Sanders, Samuel N.; Sfeir, Matthew Y.
  • Chemical Science, Vol. 10, Issue 14
  • DOI: 10.1039/C8SC03725F

25th Anniversary Article: Recent Advances in n-Type and Ambipolar Organic Field-Effect Transistors
journal, August 2013

Evidence for Singlet Fission Driven by Vibronic Coherence in Crystalline Tetracene
journal, March 2017

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

Triplet Separation Drives Singlet Fission after Femtosecond Correlated Triplet Pair Production in Rubrene
journal, August 2017

  • Breen, Ilana; Tempelaar, Roel; Bizimana, Laurie A.
  • Journal of the American Chemical Society, Vol. 139, Issue 34
  • DOI: 10.1021/jacs.7b02621

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

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

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

Singlet Exciton Fission in a Hexacene Derivative
journal, January 2013

  • Lee, Jiye; Bruzek, Matthew J.; Thompson, Nicholas J.
  • Advanced Materials, Vol. 25, Issue 10
  • DOI: 10.1002/adma.201203982

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

A molecular movie of ultrafast singlet fission
journal, September 2019

  • Schnedermann, Christoph; Alvertis, Antonios M.; Wende, Torsten
  • Nature Communications, Vol. 10, Issue 1
  • DOI: 10.1038/s41467-019-12220-7

The dependence of the absorption and fluorescence parameters, the intersystem crossing and internal conversion rate constants on the number of rings in polyacene molecules
journal, October 1997

  • Nijegorodov, N.; Ramachandran, V.; Winkoun, D. P.
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 53, Issue 11
  • DOI: 10.1016/S1386-1425(97)00071-1

Evidence for conical intersection dynamics mediating ultrafast singlet exciton fission
journal, March 2015

  • Musser, Andrew J.; Liebel, Matz; Schnedermann, Christoph
  • Nature Physics, Vol. 11, Issue 4
  • DOI: 10.1038/nphys3241

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Vibronically coherent ultrafast triplet-pair formation and subsequent thermally activated dissociation control efficient endothermic singlet fission.
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  • Stern, Hannah; Cheminal, Alexandre; Yost, Shane R.
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.30165

A molecular movie of ultrafast singlet fission.
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  • Schnedermann, Christoph; Alvertis, Antonios; Wende, Torsten
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.43274

Exploiting Excited-State Aromaticity To Design Highly Stable Singlet Fission Materials
collection, January 2019

  • Fallon, Kealan J.; Budden, Peter; Salvadori, Enrico
  • Universität des Saarlandes
  • DOI: 10.22028/d291-29308

Tuning Singlet Fission in π-Bridge-π Chromophores
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  • Kumarasamy, E.; Sanders, Sn; Tayebjee, Mjy
  • American Chemical Society
  • DOI: 10.17863/cam.13699

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  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.57369

Intramolecular Singlet Fission in Oligoacene Heterodimers
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  • Angewandte Chemie, Vol. 128, Issue 10
  • DOI: 10.1002/ange.201510632

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text, January 2017

  • Trinh, M. Tuan; Pinkard, Andrew; Pun, Andrew Brian
  • Columbia University
  • DOI: 10.7916/d8zg843k
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