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

Jue Bae, Youn; Krzyaniak, Matthew D.; Majewski, Marek B.; Desroches, Maude; Morin, Jean‐François; Wu, Yi‐Lin; Wasielewski, Michael R.

doi:10.1002/cplu.201900410

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

Journal Article · Wed Aug 21 00:00:00 EDT 2019 · ChemPlusChem

DOI:https://doi.org/10.1002/cplu.201900410· OSTI ID:1561361

Jue Bae, Youn ^[1]; Krzyaniak, Matthew D. ^[1]; Majewski, Marek B. ^[2]; Desroches, Maude ^[3]; Morin, Jean‐François ^[3]; Wu, Yi‐Lin ^[4]; ^[1]

Department of Chemistry and Institute for Sustainability and Energy at Northwestern Northwestern University Evanston IL 60208-3113 USA
Department of Chemistry and Biochemistry and Centre for NanoScience Research Concordia University Montréal Québec H4B 1R6 Canada
Department of Chemistry Université Laval Québec Québec G1 V 0 A6 Canada
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

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.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-99ER14999

OSTI ID:: 1561361

Alternate ID(s):: OSTI ID: 1610411

Journal Information:: ChemPlusChem, Journal Name: ChemPlusChem Journal Issue: 9 Vol. 84; ISSN 2192-6506

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (30)

4,10-Dibromoanthanthrone as a New Building Block for p-Type, n-Type, and Ambipolar π-Conjugated Materials Giguère, Jean-Benoît; Verolet, Quentin; Morin, Jean-François Chemistry - A European Journal, Vol. 19, Issue 1 https://doi.org/10.1002/chem.201202878	journal	November 2012
Triisopropylsilylethynyl-Functionalized Graphene-Like Fragment Semiconductors: Synthesis, Crystal Packing, and Density Functional Theory Calculations Zhang, Lei; Fonari, Alexandr; Zhang, Yue Chemistry - A European Journal, Vol. 19, Issue 52, p. 17907-17916 https://doi.org/10.1002/chem.201303308	journal	November 2013
Rational Design of Advanced Photosensitizers Based on Orthogonal BODIPY Dimers to Finely Modulate Singlet Oxygen Generation Epelde-Elezcano, Nerea; Palao, Eduardo; Manzano, Hegoi Chemistry - A European Journal, Vol. 23, Issue 20 https://doi.org/10.1002/chem.201605822	journal	March 2017
EasySpin, a comprehensive software package for spectral simulation and analysis in EPR Stoll, Stefan; Schweiger, Arthur Journal of Magnetic Resonance, Vol. 178, Issue 1, p. 42-55 https://doi.org/10.1016/j.jmr.2005.08.013	journal	January 2006
Anthanthrene Derivatives as Blue Emitting Materials for Organic Light-Emitting Diode Applications Shah, Bipin K.; Neckers, Douglas C.; Shi, Jianmin Chemistry of Materials, Vol. 18, Issue 3 https://doi.org/10.1021/cm052188x	journal	February 2006
Direct Observation of the Preference of Hole Transfer over Electron Transfer for Radical Ion Pair Recombination in Donor−Bridge−Acceptor Molecules Dance, Zachary E. X.; Ahrens, Michael J.; Vega, Amy M. Journal of the American Chemical Society, Vol. 130, Issue 3 https://doi.org/10.1021/ja077386z	journal	January 2008
Why Triple Bonds Protect Acenes from Oxidation and Decomposition Fudickar, Werner; Linker, Torsten Journal of the American Chemical Society, Vol. 134, Issue 36 https://doi.org/10.1021/ja306056x	journal	August 2012
Singlet Exciton Fission in Polycrystalline Thin Films of a Slip-Stacked Perylenediimide Eaton, Samuel W.; Shoer, Leah E.; Karlen, Steven D. Journal of the American Chemical Society, Vol. 135, Issue 39 https://doi.org/10.1021/ja4053174	journal	September 2013
Ultrafast Two-Electron Transfer in a CdS Quantum Dot–Extended-Viologen Cyclophane Complex Young, Ryan M.; Jensen, Stephen C.; Edme, Kedy Journal of the American Chemical Society, Vol. 138, Issue 19 https://doi.org/10.1021/jacs.5b13386	journal	May 2016
Singlet Fission in 9,10-Bis(phenylethynyl)anthracene Thin Films Bae, Youn Jue; Kang, Gyeongwon; Malliakas, Christos D. Journal of the American Chemical Society, Vol. 140, Issue 45 https://doi.org/10.1021/jacs.8b07498	journal	October 2018
Cruciform Alkynylated Anthanthrene Derivatives: A Structure–Properties Relationship Case Study Giguère, Jean-Benoît; Boismenu-Lavoie, Joël; Morin, Jean-François The Journal of Organic Chemistry, Vol. 79, Issue 6 https://doi.org/10.1021/jo402674m	journal	March 2014
Photophysical Properties of Anthanthrene-Based Tunable Blue Emitters Shah, Bipin K.; Neckers, Douglas C.; Shi, Jianmin The Journal of Physical Chemistry A, Vol. 109, Issue 34 https://doi.org/10.1021/jp052337z	journal	September 2005
Unified model for singlet fission within a non-conjugated covalent pentacene dimer Basel, Bettina S.; Zirzlmeier, Johannes; Hetzer, Constantin Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15171	journal	May 2017
Strongly exchange-coupled triplet pairs in an organic semiconductor Weiss, Leah R.; Bayliss, Sam L.; Kraffert, Felix Nature Physics, Vol. 13, Issue 2 https://doi.org/10.1038/nphys3908	journal	October 2016
Quintet multiexciton dynamics in singlet fission Tayebjee, Murad J. Y.; Sanders, Samuel N.; Kumarasamy, Elango Nature Physics, Vol. 13, Issue 2 https://doi.org/10.1038/nphys3909	journal	October 2016
Identifying triplet pathways in dilute pentacene films Lubert-Perquel, Daphné; Salvadori, Enrico; Dyson, Matthew Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-06330-x	journal	October 2018
Triisopropylsilylethynyl-functionalized dibenzo[def,mno]chrysene: a solution-processed small molecule for bulk heterojunction solar cells Zhang, Lei; Walker, Bright; Liu, Feng Journal of Materials Chemistry, Vol. 22, Issue 10, p. 4266-4268 https://doi.org/10.1039/C2JM14998B	journal	January 2012
Polycyclic anthanthrene small molecules: semiconductors for organic field-effect transistors and solar cells applications Giguère, Jean-Benoît; Sariciftci, Niyazi Serdar; Morin, Jean-François Journal of Materials Chemistry C, Vol. 3, Issue 3 https://doi.org/10.1039/C4TC02137A	journal	January 2015
Anthanthrene dye-sensitized solar cells: influence of the number of anchoring groups and substitution motif Geng, Yan; Yi, Chenyi; Bircher, Martin Peter RSC Advances, Vol. 5, Issue 119 https://doi.org/10.1039/C5RA21917E	journal	January 2015
Manipulating triplet states: tuning energies, absorption, lifetimes, and annihilation rates in anthanthrene derivatives Stewart, David J.; Shi, Jianmin; Naranjo, Tristan R. Physical Chemistry Chemical Physics, Vol. 20, Issue 45 https://doi.org/10.1039/C8CP06048G	journal	January 2018
Laser Generation of Excitons and Fluorescence in Anthracene Crystals Singh, S.; Jones, W. J.; Siebrand, W. The Journal of Chemical Physics, Vol. 42, Issue 1 https://doi.org/10.1063/1.1695695	journal	January 1965
Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells Shockley, William; Queisser, Hans J. Journal of Applied Physics, Vol. 32, Issue 3, p. 510-519 https://doi.org/10.1063/1.1736034	journal	March 1961
Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers Hanna, M. C.; Nozik, A. J. Journal of Applied Physics, Vol. 100, Issue 7 https://doi.org/10.1063/1.2356795	journal	October 2006
Excited state dynamics in solid and monomeric tetracene: The roles of superradiance and exciton fission Burdett, Jonathan J.; Müller, Astrid M.; Gosztola, David The Journal of Chemical Physics, Vol. 133, Issue 14 https://doi.org/10.1063/1.3495764	journal	October 2010
Quintet-triplet mixing determines the fate of the multiexciton state produced by singlet fission in a terrylenediimide dimer at room temperature Chen, Michelle; Krzyaniak, Matthew D.; Nelson, Jordan N. Proceedings of the National Academy of Sciences, Vol. 116, Issue 17 https://doi.org/10.1073/pnas.1820932116	journal	April 2019
Spin signatures of exchange-coupled triplet pairs formed by singlet fission Bayliss, Sam L.; Weiss, Leah R.; Rao, Akshay Physical Review B, Vol. 94, Issue 4 https://doi.org/10.1103/PhysRevB.94.045204	journal	July 2016
Ultrafast Exciton Relaxation in Microcrystalline Pentacene Films Marciniak, H.; Fiebig, M.; Huth, M. Physical Review Letters, Vol. 99, Issue 17 https://doi.org/10.1103/PhysRevLett.99.176402	journal	October 2007
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
A Compilation of Singlet Oxygen Yields from Biologically Relevant Molecules Redmond, Robert W.; Gamlin, Janet N. Photochemistry and Photobiology, Vol. 70, Issue 4 https://doi.org/10.1111/j.1751-1097.1999.tb08240.x	journal	October 1999
Near-transform-limited visible and near-IR femtosecond pulses from optical parametric amplification using Type II β-barium borate Greenfield, Scott R.; Wasielewski, Michael R. Optics Letters, Vol. 20, Issue 12 https://doi.org/10.1364/OL.20.001394	journal	January 1995

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