Structure and Photophysics of Indigoids for Singlet Fission: Cibalackrot

Ryerson, Joseph L.; Zaykov, Alexandr; Aguilar Suarez, Luis E.; Havenith, Remco W. A.; Stepp, Brian R.; Dron, Paul I.; Kaleta, Jirí; Akdag, Akin; Teat, Simon J.; Magnera, Thomas F.; Miller, John R.; Havlas, Zdenek; Broer, Ria; Faraji, Shirin; Michl, Josef; Johnson, Justin C.

doi:10.1063/1.5121863

Title: Structure and Photophysics of Indigoids for Singlet Fission: Cibalackrot

Journal Article · 14 November 2019 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5121863 · OSTI ID:1572370

Ryerson, Joseph L. ^[1]; Zaykov, Alexandr ^[2]; Aguilar Suarez, Luis E. ^[3];

^[3]; Stepp, Brian R. ^[4]; Dron, Paul I. ^[4]; Kaleta, Jirí ^[5]; Akdag, Akin ^[4]; Teat, Simon J. ^[6]; Magnera, Thomas F. ^[4];

^[7]; Havlas, Zdenek ^[5];

^[3]; Faraji, Shirin ^[3];

^[8];

^[9]

Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Czech Academy of Sciences, Prague (Czech Republic); Univ. of Chemistry and Technology Prague (Czech Republic)
Univ. of Groningen (Netherlands)
Univ. of Colorado, Boulder, CO (United States)
Czech Academy of Sciences, Prague (Czech Republic)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Univ. of Colorado, Boulder, CO (United States); Czech Academy of Sciences, Prague (Czech Republic)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

Here, we report an investigation of structure and photophysics of thin layers of cibalackrot, a sturdy dye derived from indigo by double annulation at the central double bond. Evaporated layers contain up to three phases, two crystalline and one amorphous. Relative amounts of all three have been determined by a combination of X-ray diffraction and FT-IR reflectance spectroscopy. Initially, excited singlet state rapidly produces a high yield of a transient intermediate whose spectral properties are compatible with charge-transfer nature. This intermediate more slowly converts to a significant yield of triplet, which, however, does not exceed 100% and may well be produced by intersystem crossing rather than singlet fission. The yields were determined by transient absorption spectroscopy and corrected for effects of partial sample alignment by a simple generally applicable procedure. Formation of excimers was also observed. Here, in order to obtain guidance for improving molecular packing by a minor structural modification, calculations by a simplified frontier orbital method were used to find all local maxima of singlet fission rate as a function of geometry of a molecular pair. The method was tested at 48 maxima by comparison with the ab initio Frenkel-Davydov exciton model.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231; AC36-08GO28308; SC0007004

OSTI ID:: 1572370

Report Number(s):: BNL--212254-2019-JAAM

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 18 Vol. 151; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

References (69)

Über neue Derivate des Indigos und anderer indigoider Farbstoffe Engi, G. Zeitschrift für Angewandte Chemie, Vol. 27, Issue 20 https://doi.org/10.1002/ange.19140272003	journal	March 1914
The Electronic Properties of Diradicals Salem, Lionel; Rowland, Colin Angewandte Chemie International Edition in English, Vol. 11, Issue 2 https://doi.org/10.1002/anie.197200921	journal	February 1972
Neutral and Charged Biradicals, Zwitterions, Funnels in S1, and Proton Translocation: Their Role in Photochemistry, Photophysics, and Vision Bonačić-Koutecký, Vlasta; Koutecký, Jaroslav; Michl, Josef Angewandte Chemie International Edition in English, Vol. 26, Issue 3 https://doi.org/10.1002/anie.198701701	journal	March 1987
Singlet Fission Tykwinski, Rik R.; Guldi, Dirk M. ChemPhotoChem, Vol. 5, Issue 5 https://doi.org/10.1002/cptc.202100053	journal	April 2021
Guidance for Mutual Disposition of Chromophores for Singlet Fission Havlas, Zdenek; Michl, Josef Israel Journal of Chemistry, Vol. 56, Issue 1 https://doi.org/10.1002/ijch.201500054	journal	October 2015
Open-Shell-Character-Based Molecular Design Principles: Applications to Nonlinear Optics and Singlet Fission Nakano, Masayoshi The Chemical Record, Vol. 17, Issue 1 https://doi.org/10.1002/tcr.201600094	journal	August 2016
Reflectance Spectroscopy Kortüm, Gustav Springer Berlin, Heidelberg https://doi.org/10.1007/978-3-642-88071-1	book	January 1969
Infrared linear dichroism of the T1 state of acridine in stretched polyethylene Mitchell, M. B.; Guillory, W. A.; Michl, J. Chemical Physics Letters, Vol. 96, Issue 4 https://doi.org/10.1016/0009-2614(83)80720-9	journal	April 1983
Reflectance spectroscopy Hunt, Graham R. Icarus, Vol. 13, Issue 3 https://doi.org/10.1016/0019-1035(70)90103-x	journal	November 1970
Polarized external infrared reflection-absorption spectrometry at the air/water interface: Comparison of experimental and theoretical results for different angles of incidence Gericke, Arne; Michailov, Alexander V.; Hühnerfuss, Heinrich Vibrational Spectroscopy, Vol. 4, Issue 3 https://doi.org/10.1016/0924-2031(93)80007-3	journal	March 1993
Optical theory applied to infrared spectroscopy Yamamoto, Kiyoshi; Ishida, Hatsuo Vibrational Spectroscopy, Vol. 8, Issue 1 https://doi.org/10.1016/0924-2031(94)00022-9	journal	November 1994
Singlet Fission: Optimization of Chromophore Dimer Geometry Buchanan, Eric A.; Havlas, Zdeněk; Michl, Josef Advances in Quantum Chemistry https://doi.org/10.1016/bs.aiq.2017.03.005	book	May 2017
Quantitative Orientation Measurements in Thin Lipid Films by Attenuated Total Reflection Infrared Spectroscopy Picard, Frédéric; Buffeteau, Thierry; Desbat, Bernard Biophysical Journal, Vol. 76, Issue 1 https://doi.org/10.1016/s0006-3495(99)77222-x	journal	January 1999
Time-dependent density functional theory within the Tamm–Dancoff approximation Hirata, So; Head-Gordon, Martin Chemical Physics Letters, Vol. 314, Issue 3-4 https://doi.org/10.1016/s0009-2614(99)01149-5	journal	December 1999
Theoretical Modeling of Singlet Fission Casanova, David Chemical Reviews, Vol. 118, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00601	journal	April 2018
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
Design Principles of Electronic Couplings for Intramolecular Singlet Fission in Covalently-Linked Systems Ito, Soichi; Nagami, Takanori; Nakano, Masayoshi The Journal of Physical Chemistry A, Vol. 120, Issue 31 https://doi.org/10.1021/acs.jpca.6b07153	journal	August 2016
Excimer Formation and Symmetry-Breaking Charge Transfer in Cofacial Perylene Dimers Cook, Rita E.; Phelan, Brian T.; Kamire, Rebecca J. The Journal of Physical Chemistry A, Vol. 121, Issue 8 https://doi.org/10.1021/acs.jpca.6b12644	journal	February 2017
Singlet Fission and Excimer Formation in Disordered Solids of Alkyl-Substituted 1,3-Diphenylisobenzofurans Dron, Paul I.; Michl, Josef; Johnson, Justin C. The Journal of Physical Chemistry A, Vol. 121, Issue 45 https://doi.org/10.1021/acs.jpca.7b07362	journal	November 2017
Beyond Shockley–Queisser: Molecular Approaches to High-Efficiency Photovoltaics Tayebjee, Murad J. Y.; McCamey, Dane R.; Schmidt, Timothy W. The Journal of Physical Chemistry Letters, Vol. 6, Issue 12 https://doi.org/10.1021/acs.jpclett.5b00716	journal	June 2015
Evidence for Singlet Fission Driven by Vibronic Coherence in Crystalline Tetracene Morrison, Adrian F.; Herbert, John M. The Journal of Physical Chemistry Letters, Vol. 8, Issue 7 https://doi.org/10.1021/acs.jpclett.7b00230	journal	March 2017
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
A Silicon–Singlet Fission Tandem Solar Cell Exceeding 100% External Quantum Efficiency with High Spectral Stability Pazos-Outón, Luis M.; Lee, Ju Min; Futscher, Moritz H. ACS Energy Letters, Vol. 2, Issue 2 https://doi.org/10.1021/acsenergylett.6b00678	journal	January 2017
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
The captodative effect Viehe, Heinz G.; Janousek, Zdenek; Merenyi, Robert Accounts of Chemical Research, Vol. 18, Issue 5 https://doi.org/10.1021/ar00113a004	journal	May 1985
The Role of Chromophore Coupling in Singlet Fission Johnson, Justin C.; Nozik, Arthur J.; Michl, Josef Accounts of Chemical Research, Vol. 46, Issue 6 https://doi.org/10.1021/ar300193r	journal	January 2013
Singlet Exciton Fission Photovoltaics Lee, Jiye; Jadhav, Priya; Reusswig, Philip D. Accounts of Chemical Research, Vol. 46, Issue 6 https://doi.org/10.1021/ar300288e	journal	April 2013
Singlet Fission Smith, Millicent B.; Michl, Josef Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr1002613	journal	November 2010
Infrared external reflection study of molecular orientation in thin Langmuir-Blodgett films Hasegawa, Takeshi; Umemura, Junzo; Takenaka, Tohru The Journal of Physical Chemistry, Vol. 97, Issue 35 https://doi.org/10.1021/j100137a028	journal	September 1993
Quantum organic photochemistry. II. Resonance and aromaticity in the lowest 3.pi..pi.* state of cyclic hydrocarbons Baird, N. Colin Journal of the American Chemical Society, Vol. 94, Issue 14 https://doi.org/10.1021/ja00769a025	journal	July 1972
Singlet Fission for Dye-Sensitized Solar Cells: Can a Suitable Sensitizer Be Found? Paci, Irina; Johnson, Justin C.; Chen, Xudong Journal of the American Chemical Society, Vol. 128, Issue 51 https://doi.org/10.1021/ja063980h	journal	December 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
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
Captodatively Stabilized Biradicaloids as Chromophores for Singlet Fission Wen, Jin; Havlas, Zdenĕk; Michl, Josef Journal of the American Chemical Society, Vol. 137, Issue 1 https://doi.org/10.1021/ja5070476	journal	December 2014
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
Packing Guidelines for Optimizing Singlet Fission Matrix Elements in Noncovalent Dimers Buchanan, Eric A.; Michl, Josef Journal of the American Chemical Society, Vol. 139, Issue 44 https://doi.org/10.1021/jacs.7b07963	journal	October 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
Exploiting Excited-State Aromaticity To Design Highly Stable Singlet Fission Materials Fallon, Kealan J.; Budden, Peter; Salvadori, Enrico Journal of the American Chemical Society, Vol. 141, Issue 35 https://doi.org/10.1021/jacs.9b06346	journal	August 2019
Photophysics of an Indigo Derivative (Keto and Leuco Structures) with Singular Properties Seixas de Melo, J.; Rondão, R.; Burrows, H. D. The Journal of Physical Chemistry A, Vol. 110, Issue 51 https://doi.org/10.1021/jp057451w	journal	December 2006
Toward Designed Singlet Fission: Solution Photophysics of Two Indirectly Coupled Covalent Dimers of 1,3-Diphenylisobenzofuran Johnson, Justin C.; Akdag, Akin; Zamadar, Matibur The Journal of Physical Chemistry B, Vol. 117, Issue 16 https://doi.org/10.1021/jp310979q	journal	November 2012
Diradical Character View of Singlet Fission Minami, Takuya; Nakano, Masayoshi The Journal of Physical Chemistry Letters, Vol. 3, Issue 2 https://doi.org/10.1021/jz2015346	journal	December 2011
Fundamental of Diradical-Character-Based Molecular Design for Singlet Fission Minami, Takuya; Ito, Soichi; Nakano, Masayoshi The Journal of Physical Chemistry Letters, Vol. 4, Issue 13 https://doi.org/10.1021/jz400931b	journal	June 2013
Quantitative Analysis of Uniaxial Molecular Orientation in Langmuir-Blodgett Films by Infrared Reflection Spectroscopy Hasegawa, T.; Takeda, S.; Kawaguchi, A. Langmuir, Vol. 11, Issue 4 https://doi.org/10.1021/la00004a032	journal	April 1995
Harnessing singlet exciton fission to break the Shockley–Queisser limit Rao, Akshay; Friend, Richard H. Nature Reviews Materials, Vol. 2, Issue 11 https://doi.org/10.1038/natrevmats.2017.63	journal	October 2017
Exciting excited-state aromaticity Ottosson, Henrik Nature Chemistry, Vol. 4, Issue 12 https://doi.org/10.1038/nchem.1518	journal	November 2012
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
Endothermic singlet fission is hindered by excimer formation Dover, Cameron B.; Gallaher, Joseph K.; Frazer, Laszlo Nature Chemistry, Vol. 10, Issue 3 https://doi.org/10.1038/nchem.2926	journal	January 2018
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
Polymorphism influences singlet fission rates in tetracene thin films Arias, Dylan H.; Ryerson, Joseph L.; Cook, Jasper D. Chemical Science, Vol. 7, Issue 2 https://doi.org/10.1039/c5sc03535j	journal	January 2016
Optimal arrangements of 1,3-diphenylisobenzofuran molecule pairs for fast singlet fission Buchanan, Eric A.; Michl, Josef Photochemical & Photobiological Sciences, Vol. 18, Issue 9 https://doi.org/10.1039/c9pp00283a	journal	January 2019
Reflection Method for Obtaining the Infrared Spectrum of a Thin Layer on a Metal Surface Greenler, Robert G. The Journal of Chemical Physics, Vol. 50, Issue 5 https://doi.org/10.1063/1.1671315	journal	March 1969
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
Infrared Study of Adsorbed Molecules on Metal Surfaces by Reflection Techniques Greenler, Robert G. The Journal of Chemical Physics, Vol. 44, Issue 1 https://doi.org/10.1063/1.1726462	journal	January 1966
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
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
Slow light enhanced singlet exciton fission solar cells with a 126% yield of electrons per photon Thompson, Nicholas J.; Congreve, Daniel N.; Goldberg, David Applied Physics Letters, Vol. 103, Issue 26 https://doi.org/10.1063/1.4858176	journal	December 2013
Singlet Exciton Fission and Tri plet-Tri plet Exciton Fusion in Crystalline Tet racene Pope, Martin; Geacintov, Nicholas E.; Vogel, Frank Molecular Crystals, Vol. 6, Issue 1 https://doi.org/10.1080/15421406908082953	journal	August 1969
Reflectance Spectroscopy Sheppard, N. Physics Bulletin, Vol. 21, Issue 6 https://doi.org/10.1088/0031-9112/21/6/026	journal	June 1970
Multiple exciton generation in quantum dots versus singlet fission in molecular chromophores for solar photon conversion Beard, Matthew C.; Johnson, Justin C.; Luther, Joseph M. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 373, Issue 2044 https://doi.org/10.1098/rsta.2014.0412	journal	June 2015
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
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
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
Kramers–Kronig analysis of infrared reflection spectra with perpendicular polarization Yamamoto, Kiyoshi; Masui, Akio; Ishida, Hatsuo Applied Optics, Vol. 33, Issue 27 https://doi.org/10.1364/ao.33.006285	journal	January 1994
Electric Fields Produced by the Propagation of Plane Coherent Electromagnetic Radiation in a Stratified Medium Hansen, Wilford N. Journal of the Optical Society of America, Vol. 58, Issue 3 https://doi.org/10.1364/josa.58.000380	journal	January 1968
Interpretation of Reflection and Transmission Spectra for Thin Films: Reflection Yamamoto, Kiyoshi; Ishida, Hatsuo Applied Spectroscopy, Vol. 48, Issue 7 https://doi.org/10.1366/0003702944029839	journal	July 1994
A Silicon–Singlet Fission Tandem Solar Cell Exceeding 100% External Quantum Efficiency with High Spectral Stability Pazos-Outón, Luis M.; Lee, Ju Min; Futscher, Moritz H. Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.9114	text	January 2017
Exploiting Excited-State Aromaticity To Design Highly Stable Singlet Fission Materials Fallon, Kealan J.; Budden, Peter; Salvadori, Enrico Universität des Saarlandes https://doi.org/10.22028/d291-29308	collection	January 2019
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

Similar Records

Competing Singlet Fission and Excimer Formation in Solid Fluorinated 1,3-Diphenylisobenzofurans

Journal Article · 2021 · Journal of Physical Chemistry C · OSTI ID:1839383

Buchanan, Eric A.; Johnson, Justin C.; Tan, Melissa; +9 more

Balancing Charge Transfer and Frenkel Exciton Coupling Leads to Excimer Formation in Molecular Dimers: Implications for Singlet Fission

Journal Article · 2020 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1798261

Bae, Youn Jue; Shimizu, Daiki; Schultz, Jonathan D.; +5 more

1,3-Diphenylisobenzofuran: a Model Chromophore for Singlet Fission

Journal Article · 2017 · Topics in Current Chemistry Collections · OSTI ID:1678685

Johnson, Justin C.; Michl, Josef

Related Subjects

14 SOLAR ENERGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Electron transfer
radiation chemistry

Title: Structure and Photophysics of Indigoids for Singlet Fission: Cibalackrot

Citation Formats

References (69)

Similar Records

Related Subjects