Manipulating Triplet Yield through Control of Symmetry-Breaking Charge Transfer

Das, Saptaparna; Thornbury, William G.; Bartynski, Andrew N.; Thompson, Mark E.; Bradforth, Stephen E.

doi:10.1021/acs.jpclett.8b01237

Manipulating Triplet Yield through Control of Symmetry-Breaking Charge Transfer

Journal Article · Thu May 31 00:00:00 EDT 2018 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.8b01237· OSTI ID:1735856

^[1]; Thornbury, William G. ^[2]; Bartynski, Andrew N. ^[2]; ^[2]; ^[2]

Univ. of Southern California, Los Angeles, CA (United States); University of Southern California
Univ. of Southern California, Los Angeles, CA (United States)

The efficiency of an organic solar cell depends on the efficacy of exciton diffusion and dissociation processes, and this can be enhanced by reducing the exciton binding energy and increasing the exciton lifetime. Zinc chlorodipyrrin (ZCl) complexes exhibit reduced exciton binding energy due to ultrafast generation of intramolecular charge transfer (ICT) states via symmetry breaking charge transfer in polar media. This paper explores the fate of the ICT states using nanosecond transient absorption. In cyclohexane, ZCl undergoes intersystem-crossing to produce triplets with ~8 ns time constant (~30% yield) and no ICT states are generated. However, in more polar solvents, triplets are generated within 1 ns via ICT state recombination with ~3 times higher yield than produced via ISC. Furthermore, this high triplet yield in toluene (89%) and acetonitrile (76%) via ICT state recombination is a beneficial pathway to spin-protect the excited state decay for additional charge generation from triplet excited states.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Southern California, Los Angeles, CA (United States)

Sponsoring Organization:: National Science Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0016450

OSTI ID:: 1735856

Alternate ID(s):: OSTI ID: 1539324

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 12 Vol. 9; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (47)

Origin of the Open Circuit Voltage of Plastic Solar Cells Brabec, C. J.; Cravino, A.; Meissner, D. Advanced Functional Materials, Vol. 11, Issue 5 https://doi.org/10.1002/1616-3028(200110)11:5<374::AID-ADFM374>3.0.CO;2-W	journal	October 2001
The exciton binding energy in luminescent conjugated polymers Brédas, Jean-Luc; Cornil, Jérôme; Heeger, Alan J. Advanced Materials, Vol. 8, Issue 5 https://doi.org/10.1002/adma.19960080517	journal	May 1996
Design Rules for Donors in Bulk-Heterojunction Tandem Solar Cells?Towards 15 % Energy-Conversion Efficiency Dennler, G.; Scharber, M. C.; Ameri, T. Advanced Materials, Vol. 20, Issue 3 https://doi.org/10.1002/adma.200702337	journal	February 2008
Polymer-Fullerene Bulk-Heterojunction Solar Cells Dennler, Gilles; Scharber, Markus C.; Brabec, Christoph J. Advanced Materials, Vol. 21, Issue 13, p. 1323-1338 https://doi.org/10.1002/adma.200801283	journal	April 2009
Magnetic-Field Effects in Organic Semiconducting Materials and Devices Hu, Bin; Yan, Liang; Shao, Ming Advanced Materials, Vol. 21, Issue 14-15 https://doi.org/10.1002/adma.200802386	journal	April 2009
25th Anniversary Article: A Decade of Organic/Polymeric Photovoltaic Research Dou, Letian; You, Jingbi; Hong, Ziruo Advanced Materials, Vol. 25, Issue 46 https://doi.org/10.1002/adma.201302563	journal	September 2013
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
Charge Separation in Excited States of Decoupled Systems?TICT Compounds and Implications Regarding the Development of New Laser Dyes and the Primary Process of Vision and Photosynthesis Rettig, Wolfgang Angewandte Chemie International Edition in English, Vol. 25, Issue 11 https://doi.org/10.1002/anie.198609711	journal	November 1986
Designing Excited States: Theory-Guided Access to Efficient Photosensitizers for Photodynamic Action Cakmak, Yusuf; Kolemen, Safacan; Duman, Selin Angewandte Chemie International Edition, Vol. 50, Issue 50 https://doi.org/10.1002/anie.201105736	journal	October 2011
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
Photoinduced Symmetry-Breaking Charge Separation Vauthey, Eric ChemPhysChem, Vol. 13, Issue 8 https://doi.org/10.1002/cphc.201200106	journal	March 2012
Optimization and simplification of polymer–fullerene solar cells through polymer and active layer design Khlyabich, Petr P.; Burkhart, Beate; Rudenko, Andrey E. Polymer, Vol. 54, Issue 20 https://doi.org/10.1016/j.polymer.2013.07.053	journal	September 2013
A brief history of the development of organic and polymeric photovoltaics Spanggaard, Holger; Krebs, Frederik C. Solar Energy Materials and Solar Cells, Vol. 83, Issue 2-3 https://doi.org/10.1016/j.solmat.2004.02.021	journal	June 2004
Triplet Excited State of BODIPY Accessed by Charge Recombination and Its Application in Triplet–Triplet Annihilation Upconversion Chen, Kepeng; Yang, Wenbo; Wang, Zhijia The Journal of Physical Chemistry A, Vol. 121, Issue 40 https://doi.org/10.1021/acs.jpca.7b07623	journal	September 2017
Charge-Transfer Excitons at Organic Semiconductor Surfaces and Interfaces Zhu, X. -Y.; Yang, Q.; Muntwiler, M. Accounts of Chemical Research, Vol. 42, Issue 11 https://doi.org/10.1021/ar800269u	journal	November 2009
Spin-orbit coupling in free-radical reactions: on the way to heavy elements Khudyakov, Igor V.; Serebrennikov, Yuri A.; Turro, Nicholas J. Chemical Reviews, Vol. 93, Issue 1 https://doi.org/10.1021/cr00017a023	journal	January 1993
Structural Changes Accompanying Intramolecular Electron Transfer: Focus on Twisted Intramolecular Charge-Transfer States and Structures Grabowski, Zbigniew R.; Rotkiewicz, Krystyna; Rettig, Wolfgang Chemical Reviews, Vol. 103, Issue 10 https://doi.org/10.1021/cr940745l	journal	October 2003
Ultrafast intersystem crossing in some intramolecular heteroexcimers Okada, Tadashi; Karaki, Ichiro; Matsuzawa, Eiji The Journal of Physical Chemistry, Vol. 85, Issue 26 https://doi.org/10.1021/j150626a002	journal	December 1981
Achieving high quantum yield charge separation in porphyrin-containing donor-acceptor molecules at 10 K Wasielewski, Michael R.; Johnson, Douglas G.; Svec, Walter A. Journal of the American Chemical Society, Vol. 110, Issue 21 https://doi.org/10.1021/ja00229a050	journal	October 1988
Spin-orbit coupling in biradicals. Ab initio MCSCF calculations on trimethylene and the methyl-methyl radical pair Carlacci, Louis; Doubleday, Charles; Furlani, Thomas R. Journal of the American Chemical Society, Vol. 109, Issue 18 https://doi.org/10.1021/ja00252a004	journal	September 1987
Charge Transport in Photofunctional Nanoparticles Self-Assembled from Zinc 5,10,15,20-Tetrakis(perylenediimide)porphyrin Building Blocks van der Boom, Tamar; Hayes, Ryan T.; Zhao, Yongyu Journal of the American Chemical Society, Vol. 124, Issue 32 https://doi.org/10.1021/ja026286k	journal	August 2002
Molecular Design and Ordering Effects in π-Functional Materials for Transistor and Solar Cell Applications Beaujuge, Pierre M.; Fréchet, Jean M. J. Journal of the American Chemical Society, Vol. 133, Issue 50, p. 20009-20029 https://doi.org/10.1021/ja2073643	journal	December 2011
On the Energetic Dependence of Charge Separation in Low-Band-Gap Polymer/Fullerene Blends Dimitrov, Stoichko D.; Bakulin, Artem A.; Nielsen, Christian B. Journal of the American Chemical Society, Vol. 134, Issue 44 https://doi.org/10.1021/ja308177d	journal	October 2012
Efficient Energy Sensitization of C ₆₀ and Application to Organic Photovoltaics Trinh, Cong; Kirlikovali, Kent O.; Bartynski, Andrew N. Journal of the American Chemical Society, Vol. 135, Issue 32 https://doi.org/10.1021/ja4043356	journal	July 2013
Symmetry-Breaking Charge Transfer in a Zinc Chlorodipyrrin Acceptor for High Open Circuit Voltage Organic Photovoltaics Bartynski, Andrew N.; Gruber, Mark; Das, Saptaparna Journal of the American Chemical Society, Vol. 137, Issue 16 https://doi.org/10.1021/jacs.5b00146	journal	April 2015
Sulfur-Bridged Terthiophene Dimers: How Sulfur Oxidation State Controls Interchromophore Electronic Coupling Cruz, Chad D.; Christensen, Peter R.; Chronister, Eric L. Journal of the American Chemical Society, Vol. 137, Issue 39 https://doi.org/10.1021/jacs.5b05457	journal	September 2015
Molecular Optimization Enables over 13% Efficiency in Organic Solar Cells Zhao, Wenchao; Li, Sunsun; Yao, Huifeng Journal of the American Chemical Society, Vol. 139, Issue 21 https://doi.org/10.1021/jacs.7b02677	journal	May 2017
Heavy Atom Free Singlet Oxygen Generation: Doubly Substituted Configurations Dominate S ₁ States of Bis-BODIPYs Duman, Selin; Cakmak, Yusuf; Kolemen, Safacan The Journal of Organic Chemistry, Vol. 77, Issue 10 https://doi.org/10.1021/jo300051v	journal	April 2012
Time-Resolved EPR Studies of Photogenerated Radical Ion Pairs Separated by p -Phenylene Oligomers and of Triplet States Resulting from Charge Recombination ^† Dance, Zachary E. X.; Mi, Qixi; McCamant, David W. The Journal of Physical Chemistry B, Vol. 110, Issue 50 https://doi.org/10.1021/jp063690n	journal	December 2006
Photosensitizer That Selectively Generates Singlet Oxygen in Nonpolar Environments: Photophysical Mechanism and Efficiency for a Covalent BODIPY Dimer Zhang, Xian-Fu; Yang, Xudong The Journal of Physical Chemistry B, Vol. 117, Issue 30 https://doi.org/10.1021/jp405102m	journal	July 2013
Symmetry-Breaking Charge Transfer of Visible Light Absorbing Systems: Zinc Dipyrrins Trinh, Cong; Kirlikovali, Kent; Das, Saptaparna The Journal of Physical Chemistry C, Vol. 118, Issue 38 https://doi.org/10.1021/jp506855t	journal	September 2014
Intersystem Crossing Mediated by Photoinduced Intramolecular Charge Transfer: Julolidine−Anthracene Molecules with Perpendicular π Systems Dance, Zachary E. X.; Mickley, Sarah M.; Wilson, Thea M. The Journal of Physical Chemistry A, Vol. 112, Issue 18 https://doi.org/10.1021/jp800561g	journal	May 2008
Triplet Formation Involving a Polar Transition State in a Well-Defined Intramolecular Perylenediimide Dimeric Aggregate Veldman, Dirk; Chopin, Stéphanie M. A.; Meskers, Stefan C. J. The Journal of Physical Chemistry A, Vol. 112, Issue 26 https://doi.org/10.1021/jp8022524	journal	July 2008
The role of spin in the kinetic control of recombination in organic photovoltaics Rao, Akshay; Chow, Philip C. Y.; Gélinas, Simon Nature, Vol. 500, Issue 7463 https://doi.org/10.1038/nature12339	journal	August 2013
Spin-dependent charge transfer state design rules in organic photovoltaics Chang, Wendi; Congreve, Daniel N.; Hontz, Eric Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7415	journal	March 2015
Bis(BF ₂ )-2,2′-bidipyrrins, a class of BODIPY dyes with new spectroscopic and photophysical properties Ventura, Barbara; Marconi, Giancarlo; Bröring, Martin New J. Chem., Vol. 33, Issue 2 https://doi.org/10.1039/B813638F	journal	January 2009
Open circuit voltage of organic solar cells: an in-depth review Elumalai, Naveen Kumar; Uddin, Ashraf Energy & Environmental Science, Vol. 9, Issue 2 https://doi.org/10.1039/C5EE02871J	journal	January 2016
Guest and solvent modulated photo-driven charge separation and triplet generation in a perylene bisimide cyclophane Spenst, Peter; Young, Ryan M.; Wasielewski, Michael R. Chemical Science, Vol. 7, Issue 8 https://doi.org/10.1039/C6SC01574C	journal	January 2016
The molecular nature of photovoltage losses in organic solar cells Schlenker, Cody W.; Thompson, Mark E. Chemical Communications, Vol. 47, Issue 13 https://doi.org/10.1039/c0cc04020g	journal	January 2011
Hetero Bodipy-dimers as heavy atom-free triplet photosensitizers showing a long-lived triplet excited state for triplet–triplet annihilation upconversion Wu, Wanhua; Cui, Xiaoneng; Zhao, Jianzhang Chemical Communications, Vol. 49, Issue 79 https://doi.org/10.1039/c3cc45470c	journal	January 2013
Magnetic-field effects on geminate radical-pair recombination Weller, Albert; Staerk, Hubert; Treichel, Rainer Faraday Discussions of the Chemical Society, Vol. 78 https://doi.org/10.1039/dc9847800271	journal	January 1984
A simple model of solvent-induced symmetry-breaking charge transfer in excited quadrupolar molecules Ivanov, Anatoly I.; Dereka, Bogdan; Vauthey, Eric The Journal of Chemical Physics, Vol. 146, Issue 16 https://doi.org/10.1063/1.4982067	journal	April 2017
Two‐layer organic photovoltaic cell Tang, C. W. Applied Physics Letters, Vol. 48, Issue 2 https://doi.org/10.1063/1.96937	journal	January 1986
Direct Determination of the Exciton Binding Energy of Conjugated Polymers Using a Scanning Tunneling Microscope Alvarado, S.; Seidler, P.; Lidzey, D. Physical Review Letters, Vol. 81, Issue 5 https://doi.org/10.1103/PhysRevLett.81.1082	journal	August 1998
The Role of Driving Energy and Delocalized States for Charge Separation in Organic Semiconductors Bakulin, A. A.; Rao, A.; Pavelyev, V. G. Science, Vol. 335, Issue 6074 https://doi.org/10.1126/science.1217745	journal	February 2012
Interfacial Charge Transfer States in Condensed Phase Systems Vandewal, Koen Annual Review of Physical Chemistry, Vol. 67, Issue 1 https://doi.org/10.1146/annurev-physchem-040215-112144	journal	May 2016
Magnetic Field Effects: MARY, MIMS and MODS* Hoff, A. J.; Gast, P.; van der Vos, R. Zeitschrift für Physikalische Chemie, Vol. 180, Issue Part_1_2 https://doi.org/10.1524/zpch.1993.180.Part_1_2.175	journal	January 1993

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Manipulating Charge‐Transfer States in BODIPYs: A Model Strategy to Rapidly Develop Photodynamic Theragnostic Agents Jiménez, Josué; Prieto‐Montero, Ruth; Maroto, Beatriz L. Chemistry – A European Journal, Vol. 26, Issue 3 https://doi.org/10.1002/chem.201904257	journal	December 2019
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