Femtosecond stimulated Raman spectroscopy – guided library mining leads to efficient singlet fission in rubrene derivatives

Bera, Kajari; Douglas, Christopher J.; Frontiera, Renee R.

doi:10.1039/D1SC04251C

Title: Femtosecond stimulated Raman spectroscopy – guided library mining leads to efficient singlet fission in rubrene derivatives

Journal Article · Wed Oct 27 00:00:00 EDT 2021 · Chemical Science

DOI:https://doi.org/10.1039/D1SC04251C· OSTI ID:1823662

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Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA

Chromophores undergoing singlet fission are promising candidates for harnessing solar energy as they can generate a pair of charge carriers by the absorption of one photon. However, photovoltaic devices employing singlet fission are still lacking practical applications due to the limitations within the existing molecules undergoing singlet fission. Chemical modifications to acenes can lead to efficient singlet fission devices, but the influence of changes to molecular structure on the rate of singlet fission is challenging to model and predict. Using femtosecond stimulated Raman spectroscopy we have previously demonstrated that the triplet separation process during singlet fission in crystalline rubrene is associated with the loss of electron density from its tetracene core. Based on this knowledge, we mined a library of new rubrene derivatives with electron withdrawing substituents that prime the molecules for efficient singlet fission, without impacting their crystal packing. Our rationally chosen crystalline chromophores exhibit significantly improved singlet fission rates. This study demonstrates the utility and strength of a structurally sensitive spectroscopic technique in providing insights to spectroscopy-guided materials selection and design guidelines that go beyond energy arguments to design new singlet fission-capable chromophores.

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Research Organization:: Univ. of Minnesota, Twin Cities, MN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0018203

OSTI ID:: 1823662

Alternate ID(s):: OSTI ID: 1856824

Journal Information:: Chemical Science, Journal Name: Chemical Science Vol. 12 Journal Issue: 41; ISSN 2041-6520

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

References (62)

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
Femtosecond Raman Microscopy Reveals Structural Dynamics Leading to Triplet Separation in Rubrene Singlet Fission Bera, Kajari; Douglas, Christopher J.; Frontiera, Renee R. The Journal of Physical Chemistry Letters, Vol. 8, Issue 23 https://doi.org/10.1021/acs.jpclett.7b02769	journal	November 2017
Femtosecond broadband stimulated Raman spectroscopy: Apparatus and methods McCamant, David W.; Kukura, Philipp; Yoon, Sangwoon Review of Scientific Instruments, Vol. 75, Issue 11 https://doi.org/10.1063/1.1807566	journal	November 2004
Synthesis and Crystal Engineering of Rubrene and Its Derivatives Clapham, Margaret L.; Murphy, Emma C.; Douglas, Christopher J. Synthesis, Vol. 53, Issue 03 https://doi.org/10.1055/s-0040-1707316	journal	October 2020
Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy Bakulin, Artem A.; Morgan, Sarah E.; Kehoe, Tom B. Nature Chemistry, Vol. 8, Issue 1 https://doi.org/10.1038/nchem.2371	journal	October 2015
Recent Advances in Singlet Fission Smith, Millicent B.; Michl, Josef Annual Review of Physical Chemistry, Vol. 64, Issue 1 https://doi.org/10.1146/annurev-physchem-040412-110130	journal	April 2013
Ultrafast Nonadiabatic Dynamics of Singlet Fission: Quantum Dynamics with the Multilayer Multiconfigurational Time-Dependent Hartree (ML-MCTDH) Method Zheng, Jie; Xie, Yu; Jiang, Shengshi The Journal of Physical Chemistry C, Vol. 120, Issue 3 https://doi.org/10.1021/acs.jpcc.5b09921	journal	January 2016
A Simple Kinetic Model for Singlet Fission: A Role of Electronic and Entropic Contributions to Macroscopic Rates Kolomeisky, Anatoly B.; Feng, Xintian; Krylov, Anna I. The Journal of Physical Chemistry C, Vol. 118, Issue 10 https://doi.org/10.1021/jp4128176	journal	February 2014
Sensitization of silicon by singlet exciton fission in tetracene Einzinger, Markus; Wu, Tony; Kompalla, Julia F. Nature, Vol. 571, Issue 7763 https://doi.org/10.1038/s41586-019-1339-4	journal	July 2019
Peak External Photocurrent Quantum Efficiency Exceeding 100% via MEG in a Quantum Dot Solar Cell Semonin, O. E.; Luther, J. M.; Choi, S. Science, Vol. 334, Issue 6062 https://doi.org/10.1126/science.1209845	journal	December 2011
Singlet Fission in Rubrene Derivatives: Impact of Molecular Packing Sutton, Christopher; Tummala, Naga Rajesh; Beljonne, David Chemistry of Materials, Vol. 29, Issue 7 https://doi.org/10.1021/acs.chemmater.6b04633	journal	March 2017
Rubrene/Fullerene Heterostructures with a Half-Gap Electroluminescence Threshold and Large Photovoltage Pandey, A. K.; Nunzi, J. -M. Advanced Materials, Vol. 19, Issue 21 https://doi.org/10.1002/adma.200701052	journal	November 2007
Femtosecond Stimulated Raman Spectroscopy Dietze, Daniel R.; Mathies, Richard A. ChemPhysChem, Vol. 17, Issue 9 https://doi.org/10.1002/cphc.201600104	journal	March 2016
Singlet Fission and Triplet Exciton Dynamics in Rubrene/Fullerene Heterojunctions: Implications for Electroluminescence Ullah, Mujeeb; Yambem, Soniya D.; Moore, Evan G. Advanced Electronic Materials, Vol. 1, Issue 12 https://doi.org/10.1002/aelm.201500229	journal	October 2015
Femtosecond Stimulated Raman Spectroscopy Kukura, Philipp; McCamant, David W.; Mathies, Richard A. Annual Review of Physical Chemistry, Vol. 58, Issue 1 https://doi.org/10.1146/annurev.physchem.58.032806.104456	journal	May 2007
Emerging Design Principles for Enhanced Solar Energy Utilization with Singlet Fission Gish, Melissa K.; Pace, Natalie A.; Rumbles, Garry The Journal of Physical Chemistry C, Vol. 123, Issue 7 https://doi.org/10.1021/acs.jpcc.8b10876	journal	January 2019
Observation of long-range exciton diffusion in highly ordered organic semiconductors Najafov, H.; Lee, B.; Zhou, Q. Nature Materials, Vol. 9, Issue 11 https://doi.org/10.1038/nmat2872	journal	October 2010
Communication: Comment on the effective temporal and spectral resolution of impulsive stimulated Raman signals Mukamel, Shaul; Biggs, Jason D. The Journal of Chemical Physics, Vol. 134, Issue 16 https://doi.org/10.1063/1.3581889	journal	April 2011
Thermally activated singlet exciton fission observed in rubrene doped organic films Zhang, Yong; Lei, Yanlian; Zhang, Qiaoming Organic Electronics, Vol. 15, Issue 2 https://doi.org/10.1016/j.orgel.2013.12.010	journal	February 2014
Harnessing Molecular Vibrations to Probe Triplet Dynamics During Singlet Fission Grieco, Christopher; Kennehan, Eric R.; Rimshaw, Adam The Journal of Physical Chemistry Letters, Vol. 8, Issue 23 https://doi.org/10.1021/acs.jpclett.7b02434	journal	November 2017
Charge Transfer–Mediated Singlet Fission Monahan, N.; Zhu, X. -Y. Annual Review of Physical Chemistry, Vol. 66, Issue 1 https://doi.org/10.1146/annurev-physchem-040214-121235	journal	April 2015
Singlet fission in rubrene single crystal: direct observation by femtosecond pump–probe spectroscopy Ma, Lin; Zhang, Keke; Kloc, Christian Physical Chemistry Chemical Physics, Vol. 14, Issue 23 https://doi.org/10.1039/c2cp40449d	journal	January 2012
Long-Lived Triplet Excited States of Bent-Shaped Pentacene Dimers by Intramolecular Singlet Fission Sakuma, Takao; Sakai, Hayato; Araki, Yasuyuki The Journal of Physical Chemistry A, Vol. 120, Issue 11 https://doi.org/10.1021/acs.jpca.6b00988	journal	March 2016
Molecular design for efficient singlet fission Ito, Soichi; Nagami, Takanori; Nakano, Masayoshi Journal of Photochemistry and Photobiology C: Photochemistry Reviews, Vol. 34 https://doi.org/10.1016/j.jphotochemrev.2018.01.002	journal	March 2018
Correlated Pair States Formed by Singlet Fission and Exciton–Exciton Annihilation Scholes, Gregory D. The Journal of Physical Chemistry A, Vol. 119, Issue 51 https://doi.org/10.1021/acs.jpca.5b09725	journal	December 2015
Observing the Multiexciton State in Singlet Fission and Ensuing Ultrafast Multielectron Transfer Chan, W. -L.; Ligges, M.; Jailaubekov, A. Science, Vol. 334, Issue 6062 https://doi.org/10.1126/science.1213986	journal	December 2011
Molecular Design Strategies for Efficient Intramolecular Singlet Exciton Fission Krishnapriya, K. C.; Musser, Andrew J.; Patil, Satish ACS Energy Letters, Vol. 4, Issue 1 https://doi.org/10.1021/acsenergylett.8b01833	journal	November 2018
Field Effect Studies on Rubrene and Impurities of Rubrene Zeis, Roswitha; Besnard, Celine; Siegrist, Theo Chemistry of Materials, Vol. 18, Issue 2 https://doi.org/10.1021/cm0502626	journal	January 2006
Fluorescence from rubrene single crystals: Interplay of singlet fission and energy trapping Ma, Lin; Zhang, Keke; Kloc, Christian Physical Review B, Vol. 87, Issue 20 https://doi.org/10.1103/PhysRevB.87.201203	journal	May 2013
Direct observation of ultrafast long-range charge separation at polymer–fullerene heterojunctions Provencher, Françoise; Bérubé, Nicolas; Parker, Anthony W. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5288	journal	July 2014
Singlet Fission in Crystalline Organic Materials: Recent Insights and Future Directions Felter, Kevin M.; Grozema, Ferdinand C. The Journal of Physical Chemistry Letters, Vol. 10, Issue 22 https://doi.org/10.1021/acs.jpclett.9b00754	journal	October 2019
Understanding the Bound Triplet-Pair State in Singlet Fission Sanders, Samuel N.; Pun, Andrew B.; Parenti, Kaia R. Chem, Vol. 5, Issue 8 https://doi.org/10.1016/j.chempr.2019.05.012	journal	August 2019
Advances in Singlet Fission Chromophore Design Enabled by Vibrational Spectroscopies Bera, Kajari; Kwang, Siu Yi; Frontiera, Renee R. The Journal of Physical Chemistry C, Vol. 124, Issue 46 https://doi.org/10.1021/acs.jpcc.0c06725	journal	October 2020
Anion Photoelectron Spectroscopy of Rubrene: Molecular Insights into Singlet Fission Energetics Tsunoyama, Hironori; Nakajima, Atsushi The Journal of Physical Chemistry C, Vol. 121, Issue 38 https://doi.org/10.1021/acs.jpcc.7b06900	journal	September 2017
Facile Background Discrimination in Femtosecond Stimulated Raman Spectroscopy Using a Dual-Frequency Raman Pump Technique Bera, Kajari; Kwang, Siu Yi; Cassabaum, Alyssa A. The Journal of Physical Chemistry A, Vol. 123, Issue 37 https://doi.org/10.1021/acs.jpca.9b02473	journal	August 2019
Re-Evaluation of Rhodopsin’s Relaxation Kinetics Determined from Femtosecond Stimulated Raman Lineshapes McCamant, David W. The Journal of Physical Chemistry B, Vol. 115, Issue 29 https://doi.org/10.1021/jp2028164	journal	June 2011
Rubrenes: Planar and Twisted Paraskar, Abhimanyu S.; Reddy, A. Ravikumar; Patra, Asit Chemistry - A European Journal, Vol. 14, Issue 34 https://doi.org/10.1002/chem.200800802	journal	October 2008
Orientation and Polarization Dependence of Ground- and Excited-State FSRS in Crystalline Betaine-30 Cassabaum, Alyssa A.; Silva, W. Ruchira; Rich, Christopher C. The Journal of Physical Chemistry C https://doi.org/10.1021/acs.jpcc.9b01023	journal	May 2019
Singlet Fission Smith, Millicent B.; Michl, Josef Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr1002613	journal	November 2010
Two-photon-induced singlet fission in rubrene single crystal Ma, Lin; Galstyan, Gegham; Zhang, Keke The Journal of Chemical Physics, Vol. 138, Issue 18 https://doi.org/10.1063/1.4804398	journal	May 2013
Partial Fluorination as a Strategy for Crystal Engineering of Rubrene Derivatives Ogden, William A.; Ghosh, Soumen; Bruzek, Matthew J. Crystal Growth & Design, Vol. 17, Issue 2 https://doi.org/10.1021/acs.cgd.6b01497	journal	January 2017
External Quantum Efficiency Above 100% in a Singlet-Exciton-Fission-Based Organic Photovoltaic Cell Congreve, D. N.; Lee, J.; Thompson, N. J. Science, Vol. 340, Issue 6130 https://doi.org/10.1126/science.1232994	journal	April 2013
Regioselective synthesis of substituted rubrenes Dodge, Jeffrey A.; Bain, J. D.; Chamberlin, A. Richard The Journal of Organic Chemistry, Vol. 55, Issue 13 https://doi.org/10.1021/jo00300a043	journal	June 1990
Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene Monahan, Nicholas R.; Sun, Dezheng; Tamura, Hiroyuki Nature Chemistry, Vol. 9, Issue 4 https://doi.org/10.1038/nchem.2665	journal	December 2016
Triplet Pair States in Singlet Fission Miyata, Kiyoshi; Conrad-Burton, Felisa S.; Geyer, Florian L. Chemical Reviews, Vol. 119, Issue 6 https://doi.org/10.1021/acs.chemrev.8b00572	journal	January 2019
Perfluorinated and Half-Fluorinated Rubrenes: Synthesis and Crystal Packing Arrangements Sakamoto, Youichi; Suzuki, Toshiyasu The Journal of Organic Chemistry, Vol. 82, Issue 15 https://doi.org/10.1021/acs.joc.7b01383	journal	July 2017
Coherent singlet fission activated by symmetry breaking Miyata, Kiyoshi; Kurashige, Yuki; Watanabe, Kazuya Nature Chemistry, Vol. 9, Issue 10 https://doi.org/10.1038/nchem.2784	journal	May 2017
The Rubrenic Synthesis: The Delicate Equilibrium between Tetracene and Cyclobutene Braga, Daniele; Jaafari, Abdelhafid; Miozzo, Luciano European Journal of Organic Chemistry, Vol. 2011, Issue 22 https://doi.org/10.1002/ejoc.201100033	journal	May 2011
Rubrene-Based Single-Crystal Organic Semiconductors: Synthesis, Electronic Structure, and Charge-Transport Properties McGarry, Kathryn A.; Xie, Wei; Sutton, Christopher Chemistry of Materials, Vol. 25, Issue 11 https://doi.org/10.1021/cm400736s	journal	May 2013
Structural Observation of the Primary Isomerization in Vision with Femtosecond-Stimulated Raman Kukura, P. Science, Vol. 310, Issue 5750 https://doi.org/10.1126/science.1118379	journal	November 2005
Probing Interfacial Electron Transfer in Coumarin 343 Sensitized TiO ₂ Nanoparticles with Femtosecond Stimulated Raman Frontiera, Renee R.; Dasgupta, Jyotishman; Mathies, Richard A. Journal of the American Chemical Society, Vol. 131, Issue 43 https://doi.org/10.1021/ja907188b	journal	November 2009
Connecting Molecular Structure and Exciton Diffusion Length in Rubrene Derivatives Mullenbach, Tyler K.; McGarry, Kathryn A.; Luhman, Wade A. Advanced Materials, Vol. 25, Issue 27 https://doi.org/10.1002/adma.201300641	journal	June 2013
Mapping GFP structure evolution during proton transfer with femtosecond Raman spectroscopy Fang, Chong; Frontiera, Renee R.; Tran, Rosalie Nature, Vol. 462, Issue 7270 https://doi.org/10.1038/nature08527	journal	November 2009
Recent Highlights and Perspectives on Acene Based Molecules and Materials Ye, Qun; Chi, Chunyan Chemistry of Materials, Vol. 26, Issue 14 https://doi.org/10.1021/cm501536p	journal	July 2014
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
Triplet Separation Drives Singlet Fission after Femtosecond Correlated Triplet Pair Production in Rubrene Breen, Ilana; Tempelaar, Roel; Bizimana, Laurie A. Journal of the American Chemical Society, Vol. 139, Issue 34 https://doi.org/10.1021/jacs.7b02621	journal	August 2017
Femtosecond Stimulated Raman Spectroscopy Kukura, Philipp; Yoon, Sangwoon; Mathies, Richard A. Analytical Chemistry, Vol. 78, Issue 17 https://doi.org/10.1021/ac069450l	journal	September 2006
Singlet Fission: From Coherences to Kinetics Piland, Geoffrey B.; Burdett, Jonathan J.; Dillon, Robert J. The Journal of Physical Chemistry Letters, Vol. 5, Issue 13 https://doi.org/10.1021/jz500676c	journal	June 2014
The entangled triplet pair state in acene and heteroacene materials Yong, Chaw Keong; Musser, Andrew J.; Bayliss, Sam L. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15953	journal	July 2017
Ultrafast Raman Spectroscopy as a Probe of Local Structure and Dynamics in Photoexcited Conjugated Materials Bragg, Arthur E.; Yu, Wenjian; Zhou, Jiawang The Journal of Physical Chemistry Letters, Vol. 7, Issue 19 https://doi.org/10.1021/acs.jpclett.6b01060	journal	September 2016
Evidence for conical intersection dynamics mediating ultrafast singlet exciton fission Musser, Andrew J.; Liebel, Matz; Schnedermann, Christoph Nature Physics, Vol. 11, Issue 4 https://doi.org/10.1038/nphys3241	journal	March 2015
Competition between polaron pair formation and singlet fission observed in amorphous rubrene films Jankus, Vygintas; Snedden, Edward W.; Bright, Daniel W. Physical Review B, Vol. 87, Issue 22 https://doi.org/10.1103/PhysRevB.87.224202	journal	June 2013

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