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

Bae, Youn Jue; Christensen, Joseph A.; Kang, Gyeongwon; Zhou, Jiawang; Young, Ryan M.; Wu, Yi-Lin; Van Duyne, Richard P.; Schatz, George C.; Wasielewski, Michael R.

doi:10.1063/1.5110411

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

Journal Article · Thu Jul 25 00:00:00 EDT 2019 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5110411· OSTI ID:1610423

^[1]; Christensen, Joseph A. ^[2]; ^[2]; ^[2]; Young, Ryan M. ^[2]; ^[2]; Van Duyne, Richard P. ^[2]; ^[2]; ^[2]

Northwestern Univ., Evanston, IL (United States); DOE/OSTI
Northwestern Univ., Evanston, IL (United States)

Singlet fission (SF) converts a singlet exciton into two triplet excitons in two or more electronically coupled organic chromophores, which may then be used to increase solar cell efficiency. Many known SF chromophores are unsuitable for device applications due to chemical instability or low triplet state energies. The results described here show that efficient SF occurs in derivatives of 9,10-bis(phenylethynyl)anthracene (BPEA), which is a highly robust and tunable chromophore. Fluoro and methoxy substituents at the 4- and 4'-positions of the BPEA phenyl groups control the intermolecular packing in the crystal structure, which alters the interchromophore electronic coupling, while also changing the SF energetics. The lowest excited singlet state (S₁) energy of 4,4'-difluoro-BPEA is higher than that of BPEA so that the increased thermodynamic favorability of SF results in a (16 ± 2 ps)^-1 SF rate and a 180% ± 16% triplet yield, which is about an order of magnitude faster than BPEA with a comparable triplet yield. By contrast, 4-fluoro-4'-methoxy-BPEA and 4,4'-dimethoxy-BPEA have slower SF rates, (90 ± 20 ps)^-1 and (120 ± 10 ps)^-1, and lower triplet yields, (110 ± 4)% and (168 ± 7)%, respectively, than 4,4'-difluoro-BPEA. These differences are attributed to changes in the crystal structure controlling interchromophore electronic coupling as well as SF energetics in these polycrystalline solids.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FG02-99ER14999; SC0001059

OSTI ID:: 1610423

Alternate ID(s):: OSTI ID: 1544909

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 4 Vol. 151; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (49)

Chemistry with ADF te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J. Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967 https://doi.org/10.1002/jcc.1056	journal	January 2001
Evidence for Charge-Transfer Mediation in the Primary Events of Singlet Fission in a Weakly Coupled Pentacene Dimer Basel, Bettina S.; Zirzlmeier, Johannes; Hetzer, Constantin Chem, Vol. 4, Issue 5 https://doi.org/10.1016/j.chempr.2018.04.006	journal	May 2018
Molecular Aggregate Photophysics beyond the Kasha Model: Novel Design Principles for Organic Materials Hestand, Nicholas J.; Spano, Frank C. Accounts of Chemical Research, Vol. 50, Issue 2 https://doi.org/10.1021/acs.accounts.6b00576	journal	January 2017
Effects of Crystal Morphology on Singlet Exciton Fission in Diketopyrrolopyrrole Thin Films Hartnett, Patrick E.; Margulies, Eric A.; Mauck, Catherine M. The Journal of Physical Chemistry B, Vol. 120, Issue 7 https://doi.org/10.1021/acs.jpcb.5b10565	journal	February 2016
Excited-State Dynamics of Diindenoperylene in Liquid Solution and in Solid Films Nichols, Valerie M.; Broch, Katharina; Schreiber, Frank The Journal of Physical Chemistry C, Vol. 119, Issue 23 https://doi.org/10.1021/acs.jpcc.5b03353	journal	June 2015
Morphological Evolution and Singlet Fission in Aqueous Suspensions of TIPS-Pentacene Nanoparticles Tayebjee, Murad J. Y.; Schwarz, Kyra N.; MacQueen, Rowan W. The Journal of Physical Chemistry C, Vol. 120, Issue 1 https://doi.org/10.1021/acs.jpcc.5b11353	journal	December 2015
Modeling Singlet Fission in Rylene and Diketopyrrolopyrrole Derivatives: The Role of the Charge Transfer State in Superexchange and Excimer Formation Miller, Claire E.; Wasielewski, Michael R.; Schatz, George C. The Journal of Physical Chemistry C, Vol. 121, Issue 19 https://doi.org/10.1021/acs.jpcc.7b02697	journal	May 2017
Substituent Effects on Singlet Exciton Fission in Polycrystalline Thin Films of Cyano-Substituted Diaryltetracenes Margulies, Eric A.; Kerisit, Nicolas; Gawel, Przemyslaw The Journal of Physical Chemistry C, Vol. 121, Issue 39 https://doi.org/10.1021/acs.jpcc.7b07870	journal	September 2017
Ultrafast Singlet Exciton Fission Dynamics in 9,10-Bis(phenylethynyl)anthracene Nanoaggregates and Thin Films Manna, Biswajit; Nandi, Amitabha; Ghosh, Rajib The Journal of Physical Chemistry C, Vol. 122, Issue 36 https://doi.org/10.1021/acs.jpcc.8b05260	journal	August 2018
Molecular Packing and Singlet Fission: The Parent and Three Fluorinated 1,3-Diphenylisobenzofurans Buchanan, Eric A.; Kaleta, Jiří; Wen, Jin The Journal of Physical Chemistry Letters, Vol. 10, Issue 8 https://doi.org/10.1021/acs.jpclett.8b03875	journal	March 2019
Luminescent Liquid Crystals Derived from 9,10-Bis(Phenylethynyl)anthracene Giménez, Raquel; Piñol, Milagros; Serrano, José Luis Chemistry of Materials, Vol. 16, Issue 7 https://doi.org/10.1021/cm030582u	journal	April 2004
Synthesis and photoproperties of diamagnetic octabutoxyphthalocyanines with deep red optical absorbance Rihter, Boris D.; Kenney, Malcolm E.; Ford, William E. Journal of the American Chemical Society, Vol. 112, Issue 22 https://doi.org/10.1021/ja00178a032	journal	October 1990
High Triplet Yield from Singlet Fission in a Thin Film of 1,3-Diphenylisobenzofuran Johnson, Justin C.; Nozik, Arthur J.; Michl, Josef Journal of the American Chemical Society, Vol. 132, Issue 46 https://doi.org/10.1021/ja104123r	journal	November 2010
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
Geometry and Electronic Coupling in Perylenediimide Stacks: Mapping Structure−Charge Transport Relationships Vura-Weis, Josh; Ratner, Mark A.; Wasielewski, Michael R. Journal of the American Chemical Society, Vol. 132, Issue 6 https://doi.org/10.1021/ja907761e	journal	February 2010
Charge Transport across DNA-Based Three-Way Junctions Young, Ryan M.; Singh, Arunoday P. N.; Thazhathveetil, Arun K. Journal of the American Chemical Society, Vol. 137, Issue 15 https://doi.org/10.1021/jacs.5b00931	journal	April 2015
Singlet Fission via an Excimer-Like Intermediate in 3,6-Bis(thiophen-2-yl)diketopyrrolopyrrole Derivatives Mauck, Catherine M.; Hartnett, Patrick E.; Margulies, Eric A. Journal of the American Chemical Society, Vol. 138, Issue 36 https://doi.org/10.1021/jacs.6b05627	journal	August 2016
Direct Observation of a Charge-Transfer State Preceding High-Yield Singlet Fission in Terrylenediimide Thin Films Margulies, Eric A.; Logsdon, Jenna L.; Miller, Claire E. Journal of the American Chemical Society, Vol. 139, Issue 2 https://doi.org/10.1021/jacs.6b07721	journal	December 2016
Bandgap Engineering in π-Extended Pyrroles. A Modular Approach to Electron-Deficient Chromophores with Multi-Redox Activity Zhylitskaya, Halina; Cybińska, Joanna; Chmielewski, Piotr Journal of the American Chemical Society, Vol. 138, Issue 35 https://doi.org/10.1021/jacs.6b07826	journal	August 2016
Tuning Singlet Fission in π-Bridge-π Chromophores Kumarasamy, Elango; Sanders, Samuel N.; Tayebjee, Murad J. Y. Journal of the American Chemical Society, Vol. 139, Issue 36 https://doi.org/10.1021/jacs.7b05204	journal	September 2017
Singlet Fission Involves an Interplay between Energetic Driving Force and Electronic Coupling in Perylenediimide Films Le, Aaron K.; Bender, Jon A.; Arias, Dylan H. Journal of the American Chemical Society, Vol. 140, Issue 2 https://doi.org/10.1021/jacs.7b11888	journal	January 2018
Singlet Fission in Covalent Terrylenediimide Dimers: Probing the Nature of the Multiexciton State Using Femtosecond Mid-Infrared Spectroscopy Chen, Michelle; Bae, Youn Jue; Mauck, Catherine M. Journal of the American Chemical Society, Vol. 140, Issue 29 https://doi.org/10.1021/jacs.8b04830	journal	June 2018
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
Two-Dimensional Electronic Spectroscopy Reveals Excitation Energy-Dependent State Mixing during Singlet Fission in a Terrylenediimide Dimer Mandal, Aritra; Chen, Michelle; Foszcz, Eileen D. Journal of the American Chemical Society, Vol. 140, Issue 51 https://doi.org/10.1021/jacs.8b08627	journal	December 2018
Photoinduced Charge Separation in Two Bis(phenylethynyl)anthracene-Based Triads: Inverted Region Effect vs Distance Effect on Back Electron Transfer Suneesh, Chettiyam Veettil; Vinayak, Manikkedath Viswanathan; Gopidas, Karical R. The Journal of Physical Chemistry C, Vol. 114, Issue 43 https://doi.org/10.1021/jp107607f	journal	October 2010
Photophysical Properties of 9,10-Disubstituted Anthracene Derivatives in Solution and Films Ribierre, J. C.; Ruseckas, A.; Cavaye, H. The Journal of Physical Chemistry A, Vol. 115, Issue 26 https://doi.org/10.1021/jp200668x	journal	July 2011
Theoretical Investigation of Singlet Fission in Molecular Dimers: The Role of Charge Transfer States and Quantum Interference Mirjani, Fatemeh; Renaud, Nicolas; Gorczak, Natalie The Journal of Physical Chemistry C, Vol. 118, Issue 26 https://doi.org/10.1021/jp503398a	journal	June 2014
First Steps in Photophysics. I. Fluorescence Yield and Radiative Rate Coefficient of 9,10-Bis(phenylethynyl)anthracene in Paraffins Demeter, Attila The Journal of Physical Chemistry A, Vol. 118, Issue 43 https://doi.org/10.1021/jp507626h	journal	October 2014
Mapping the Relation between Stacking Geometries and Singlet Fission Yield in a Class of Organic Crystals Renaud, Nicolas; Sherratt, Paul A.; Ratner, Mark A. The Journal of Physical Chemistry Letters, Vol. 4, Issue 7 https://doi.org/10.1021/jz400176m	journal	March 2013
Impact of Intermolecular Distance on Singlet Fission in a Series of TIPS Pentacene Compounds Wu, Yishi; Liu, Ke; Liu, Huiying The Journal of Physical Chemistry Letters, Vol. 5, Issue 20 https://doi.org/10.1021/jz5017729	journal	September 2014
Enabling singlet fission by controlling intramolecular charge transfer in π-stacked covalent terrylenediimide dimers Margulies, Eric A.; Miller, Claire E.; Wu, Yilei Nature Chemistry, Vol. 8, Issue 12 https://doi.org/10.1038/nchem.2589	journal	August 2016
Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering Lukman, Steven; Chen, Kai; Hodgkiss, Justin M. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13622	journal	December 2016
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
A design strategy for intramolecular singlet fission mediated by charge-transfer states in donor–acceptor organic materials Busby, Erik; Xia, Jianlong; Wu, Qin Nature Materials, Vol. 14, Issue 4 https://doi.org/10.1038/nmat4175	journal	January 2015
Robust singlet fission in pentacene thin films with tuned charge transfer interactions Broch, K.; Dieterle, J.; Branchi, F. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03300-1	journal	March 2018
π-extended anthracenes as sensitive probes for mechanical stress Göstl, R.; Sijbesma, R. P. Chemical Science, Vol. 7, Issue 1 https://doi.org/10.1039/c5sc03297k	journal	January 2016
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
Microscopic theory of singlet exciton fission. II. Application to pentacene dimers and the role of superexchange Berkelbach, Timothy C.; Hybertsen, Mark S.; Reichman, David R. The Journal of Chemical Physics, Vol. 138, Issue 11 https://doi.org/10.1063/1.4794427	journal	March 2013
Singlet fission in pentacene dimers Zirzlmeier, Johannes; Lehnherr, Dan; Coto, Pedro B. Proceedings of the National Academy of Sciences, Vol. 112, Issue 17 https://doi.org/10.1073/pnas.1422436112	journal	April 2015
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
DRF90: a polarizable force field Swart, M.; van Duijnen, P. Th. Molecular Simulation, Vol. 32, Issue 6 https://doi.org/10.1080/08927020600631270	journal	May 2006
Photophysics of pentacene thin films: The role of exciton fission and heating effects Rao, Akshay; Wilson, Mark W. B.; Albert-Seifried, Sebastian Physical Review B, Vol. 84, Issue 19 https://doi.org/10.1103/physrevb.84.195411	journal	November 2011
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
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
π-extended anthracenes as sensitive probes for mechanical stress Göstl, Robert; Sijbesma, Rint P. Unpublished https://doi.org/10.13140/rg.2.1.2680.8805	text	January 2015
Tuning Singlet Fission in π-Bridge-π Chromophores Kumarasamy, E.; Sanders, Sn; Tayebjee, Mjy American Chemical Society https://doi.org/10.17863/cam.13699	journalarticle	January 2017
Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering Lukman, Steven; Chen, K.; Hodgkiss, Jm Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.6798	text	January 2016
Microscopic theory of singlet exciton fission. II. Application to pentacene dimers and the role of superexchange Berkelbach, Timothy C.; Hybertsen, Mark S.; Reichman, David R. arXiv https://doi.org/10.48550/arxiv.1211.6459	text	January 2012

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