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Title: Competition between Singlet Fission and Spin‐Orbit‐Induced Intersystem Crossing in Anthanthrene and Anthanthrone Derivatives

Abstract

Abstract Singlet and triplet excited‐state dynamics of anthanthrene and anthanthrone derivatives in solution are studied. Triisopropylsilyl‐ (TIPS) or H‐terminated ethynyl groups are used to tune the singlet and triplet energies to enable their potential applications in singlet fission and triplet fusion processes. Time‐resolved optical and electron paramagnetic resonance (EPR) spectroscopies are used to obtain a mechanistic understanding of triplet formation. The anthanthrene derivatives form triplet states efficiently at a rate (ca. 10 7  s −1 ) comparable to radiative singlet fluorescence processes with approximately 30 % triplet yields, despite their large S 1 ‐T 1 energy gap (>1 eV) and the lack of carbonyl groups. In contrast, anthanthrone has a higher triplet yield (50±10 %) with a faster intersystem crossing rate (2.7 10 8  s −1 ) because of the n‐π* character of the S 1 ←S 0 transition. Analysis of time‐resolved spin‐polarized EPR spectra of these compounds reveals that the triplet states are primarily generated by the spin‐orbit‐induced intersystem crossing mechanism. However, at high concentrations, the EPR spectrum of the 4,6,10,14‐tetrakis(TIPS‐ethynyl)anthanthrene triplet state shows a significant contribution from a non‐Boltzmann population of the m s =0 spin sublevel, which is characteristic of triplet formation by singlet fission.

Authors:
 [1];  [1];  [2];  [3];  [3];  [4]; ORCiD logo [1]
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  1. Department of Chemistry and Institute for Sustainability and Energy at Northwestern Northwestern University Evanston IL 60208-3113 USA
  2. Department of Chemistry and Biochemistry and Centre for NanoScience Research Concordia University Montréal Québec H4B 1R6 Canada
  3. Department of Chemistry Université Laval Québec Québec G1 V 0 A6 Canada
  4. Department of Chemistry and Institute for Sustainability and Energy at Northwestern Northwestern University Evanston IL 60208-3113 USA, School of Chemistry Cardiff University Main Building, Park Place Cardiff CF10 3AT United Kingdom
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1561361
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
ChemPlusChem
Additional Journal Information:
Journal Name: ChemPlusChem Journal Volume: 84 Journal Issue: 9; Journal ID: ISSN 2192-6506
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Jue Bae, Youn, Krzyaniak, Matthew D., Majewski, Marek B., Desroches, Maude, Morin, Jean‐François, Wu, Yi‐Lin, and Wasielewski, Michael R. Competition between Singlet Fission and Spin‐Orbit‐Induced Intersystem Crossing in Anthanthrene and Anthanthrone Derivatives. Germany: N. p., 2019. Web. doi:10.1002/cplu.201900410.
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Jue Bae, Youn, Krzyaniak, Matthew D., Majewski, Marek B., Desroches, Maude, Morin, Jean‐François, Wu, Yi‐Lin, & Wasielewski, Michael R. Competition between Singlet Fission and Spin‐Orbit‐Induced Intersystem Crossing in Anthanthrene and Anthanthrone Derivatives. Germany. https://doi.org/10.1002/cplu.201900410
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Jue Bae, Youn, Krzyaniak, Matthew D., Majewski, Marek B., Desroches, Maude, Morin, Jean‐François, Wu, Yi‐Lin, and Wasielewski, Michael R. Wed . "Competition between Singlet Fission and Spin‐Orbit‐Induced Intersystem Crossing in Anthanthrene and Anthanthrone Derivatives". Germany. https://doi.org/10.1002/cplu.201900410.
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@article{osti_1561361,
title = {Competition between Singlet Fission and Spin‐Orbit‐Induced Intersystem Crossing in Anthanthrene and Anthanthrone Derivatives},
author = {Jue Bae, Youn and Krzyaniak, Matthew D. and Majewski, Marek B. and Desroches, Maude and Morin, Jean‐François and Wu, Yi‐Lin and Wasielewski, Michael R.},
abstractNote = {Abstract Singlet and triplet excited‐state dynamics of anthanthrene and anthanthrone derivatives in solution are studied. Triisopropylsilyl‐ (TIPS) or H‐terminated ethynyl groups are used to tune the singlet and triplet energies to enable their potential applications in singlet fission and triplet fusion processes. Time‐resolved optical and electron paramagnetic resonance (EPR) spectroscopies are used to obtain a mechanistic understanding of triplet formation. The anthanthrene derivatives form triplet states efficiently at a rate (ca. 10 7  s −1 ) comparable to radiative singlet fluorescence processes with approximately 30 % triplet yields, despite their large S 1 ‐T 1 energy gap (>1 eV) and the lack of carbonyl groups. In contrast, anthanthrone has a higher triplet yield (50±10 %) with a faster intersystem crossing rate (2.7 10 8  s −1 ) because of the n‐π* character of the S 1 ←S 0 transition. Analysis of time‐resolved spin‐polarized EPR spectra of these compounds reveals that the triplet states are primarily generated by the spin‐orbit‐induced intersystem crossing mechanism. However, at high concentrations, the EPR spectrum of the 4,6,10,14‐tetrakis(TIPS‐ethynyl)anthanthrene triplet state shows a significant contribution from a non‐Boltzmann population of the m s =0 spin sublevel, which is characteristic of triplet formation by singlet fission.},
doi = {10.1002/cplu.201900410},
journal = {ChemPlusChem},
number = 9,
volume = 84,
place = {Germany},
year = {Wed Aug 21 00:00:00 EDT 2019},
month = {Wed Aug 21 00:00:00 EDT 2019}
}
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https://doi.org/10.1002/cplu.201900410
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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

4,10-Dibromoanthanthrone as a New Building Block for p-Type, n-Type, and Ambipolar π-Conjugated Materials
journal, November 2012

  • Giguère, Jean-Benoît; Verolet, Quentin; Morin, Jean-François
  • Chemistry - A European Journal, Vol. 19, Issue 1
  • DOI: 10.1002/chem.201202878

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

Ultrafast Two-Electron Transfer in a CdS Quantum Dot–Extended-Viologen Cyclophane Complex
journal, May 2016

  • Young, Ryan M.; Jensen, Stephen C.; Edme, Kedy
  • Journal of the American Chemical Society, Vol. 138, Issue 19
  • DOI: 10.1021/jacs.5b13386

Polycyclic anthanthrene small molecules: semiconductors for organic field-effect transistors and solar cells applications
journal, January 2015

  • Giguère, Jean-Benoît; Sariciftci, Niyazi Serdar; Morin, Jean-François
  • Journal of Materials Chemistry C, Vol. 3, Issue 3
  • DOI: 10.1039/C4TC02137A

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

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

Ultrafast Exciton Relaxation in Microcrystalline Pentacene Films
journal, October 2007

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

Near-transform-limited visible and near-IR femtosecond pulses from optical parametric amplification using Type II β-barium borate
journal, January 1995

  • Greenfield, Scott R.; Wasielewski, Michael R.
  • Optics Letters, Vol. 20, Issue 12
  • DOI: 10.1364/OL.20.001394

Spin signatures of exchange-coupled triplet pairs formed by singlet fission
journal, July 2016

A Compilation of Singlet Oxygen Yields from Biologically Relevant Molecules
journal, October 1999

Direct Observation of the Preference of Hole Transfer over Electron Transfer for Radical Ion Pair Recombination in Donor−Bridge−Acceptor Molecules
journal, January 2008

  • Dance, Zachary E. X.; Ahrens, Michael J.; Vega, Amy M.
  • Journal of the American Chemical Society, Vol. 130, Issue 3
  • DOI: 10.1021/ja077386z

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

Rational Design of Advanced Photosensitizers Based on Orthogonal BODIPY Dimers to Finely Modulate Singlet Oxygen Generation
journal, March 2017

  • Epelde-Elezcano, Nerea; Palao, Eduardo; Manzano, Hegoi
  • Chemistry - A European Journal, Vol. 23, Issue 20
  • DOI: 10.1002/chem.201605822

Why Triple Bonds Protect Acenes from Oxidation and Decomposition
journal, August 2012

  • Fudickar, Werner; Linker, Torsten
  • Journal of the American Chemical Society, Vol. 134, Issue 36
  • DOI: 10.1021/ja306056x

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

Triisopropylsilylethynyl-Functionalized Graphene-Like Fragment Semiconductors: Synthesis, Crystal Packing, and Density Functional Theory Calculations
journal, November 2013

  • Zhang, Lei; Fonari, Alexandr; Zhang, Yue
  • Chemistry - A European Journal, Vol. 19, Issue 52, p. 17907-17916
  • DOI: 10.1002/chem.201303308

Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells
journal, March 1961

  • Shockley, William; Queisser, Hans J.
  • Journal of Applied Physics, Vol. 32, Issue 3, p. 510-519
  • DOI: 10.1063/1.1736034

Anthanthrene Derivatives as Blue Emitting Materials for Organic Light-Emitting Diode Applications
journal, February 2006

  • Shah, Bipin K.; Neckers, Douglas C.; Shi, Jianmin
  • Chemistry of Materials, Vol. 18, Issue 3
  • DOI: 10.1021/cm052188x

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

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

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

Photophysical Properties of Anthanthrene-Based Tunable Blue Emitters
journal, September 2005

  • Shah, Bipin K.; Neckers, Douglas C.; Shi, Jianmin
  • The Journal of Physical Chemistry A, Vol. 109, Issue 34
  • DOI: 10.1021/jp052337z

Manipulating triplet states: tuning energies, absorption, lifetimes, and annihilation rates in anthanthrene derivatives
journal, January 2018

  • Stewart, David J.; Shi, Jianmin; Naranjo, Tristan R.
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 45
  • DOI: 10.1039/C8CP06048G

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

Anthanthrene dye-sensitized solar cells: influence of the number of anchoring groups and substitution motif
journal, January 2015

  • Geng, Yan; Yi, Chenyi; Bircher, Martin Peter
  • RSC Advances, Vol. 5, Issue 119
  • DOI: 10.1039/C5RA21917E

Triisopropylsilylethynyl-functionalized dibenzo[def,mno]chrysene: a solution-processed small molecule for bulk heterojunction solar cells
journal, January 2012

  • Zhang, Lei; Walker, Bright; Liu, Feng
  • Journal of Materials Chemistry, Vol. 22, Issue 10, p. 4266-4268
  • DOI: 10.1039/C2JM14998B

Cruciform Alkynylated Anthanthrene Derivatives: A Structure–Properties Relationship Case Study
journal, March 2014

  • Giguère, Jean-Benoît; Boismenu-Lavoie, Joël; Morin, Jean-François
  • The Journal of Organic Chemistry, Vol. 79, Issue 6
  • DOI: 10.1021/jo402674m

Excited state dynamics in solid and monomeric tetracene: The roles of superradiance and exciton fission
journal, October 2010

  • Burdett, Jonathan J.; Müller, Astrid M.; Gosztola, David
  • The Journal of Chemical Physics, Vol. 133, Issue 14
  • DOI: 10.1063/1.3495764
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