Charge Separation Mechanisms in Ordered Films of Self-Assembled Donor–Acceptor Dyad Ribbons

Logsdon, Jenna L.; Hartnett, Patrick E.; Nelson, Jordan N.; Harris, Michelle A.; Marks, Tobin J.; Wasielewski, Michael R.

doi:10.1021/acsami.7b02585

Title: Charge Separation Mechanisms in Ordered Films of Self-Assembled Donor–Acceptor Dyad Ribbons

Journal Article · Fri Apr 21 00:00:00 EDT 2017 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.7b02585· OSTI ID:1399126

Logsdon, Jenna L. ^[1]; Hartnett, Patrick E. ^[1]; Nelson, Jordan N. ^[1]; Harris, Michelle A. ^[1];

^[1];

^[1]

Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER); Northwestern Univ., Evanston, IL (United States)

Orthogonal attachment of polar and nonpolar side-chains to a zinc porphyrin-perylenediimide dyad (ZnP-PDI, 1a) is shown herein to result in self-assembly of ordered supramolecular ribbons in which the ZnP and PDI molecules form segregated $$π$$-stacked columns. Following photoexcitation of the ordered ribbons, ZnP^+•-PDI^–• radical ion pairs form in <200 fs and subsequently produce a 30 ± 3% yield of free charge carriers that live for about 100 μs. Elongating the side chains on ZnP and PDI in 1b enhances the order of the films, but does not result in an increase in free charge carrier yield. In addition, this yield is independent of temperature, free energy of reaction, and the ZnP-PDI distance in the covalent dyad. These results suggest that the free charge carrier yield in this system is not limited by a bound charge transfer (CT) state or promoted by a vibronically hot CT state. Instead, it is likely that π-stacking of the segregated donors and acceptors within the ribbons results in delocalization of the charges following photoexcitation, allowing them to overcome Coulombic attraction and generate free charge carriers.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)

Grant/Contract Number:: FG02-99ER14999; DGE-1324585

OSTI ID:: 1399126

Journal Information:: ACS Applied Materials and Interfaces, Vol. 9, Issue 39; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 16 works

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References (65)

Polymer Photovoltaic Cells: Enhanced Efficiencies via a Network of Internal Donor-Acceptor Heterojunctions Yu, G.; Gao, J.; Hummelen, J. C. Science, Vol. 270, Issue 5243, p. 1789-1791 https://doi.org/10.1126/science.270.5243.1789	journal	December 1995
Conjugated Polymer-Based Organic Solar Cells Günes, Serap; Neugebauer, Helmut; Sariciftci, Niyazi Serdar Chemical Reviews, Vol. 107, Issue 4, p. 1324-1338 https://doi.org/10.1021/cr050149z	journal	April 2007
On the Efficiency Limit of Conjugated Polymer:Fullerene-Based Bulk Heterojunction Solar Cells Scharber, Markus C. Advanced Materials, Vol. 28, Issue 10 https://doi.org/10.1002/adma.201504914	journal	January 2016
Charge generation in organic photovoltaics: a review of theory and computation Pelzer, Kenley M.; Darling, Seth B. Molecular Systems Design & Engineering, Vol. 1, Issue 1 https://doi.org/10.1039/C6ME00005C	journal	January 2016
Charge Photogeneration in Organic Solar Cells Clarke, Tracey M.; Durrant, James R. Chemical Reviews, Vol. 110, Issue 11, p. 6736-6767 https://doi.org/10.1021/cr900271s	journal	November 2010
Mesoscopic Features of Charge Generation in Organic Semiconductors Savoie, Brett M.; Jackson, Nicholas E.; Chen, Lin X. Accounts of Chemical Research, Vol. 47, Issue 11 https://doi.org/10.1021/ar5000852	journal	July 2014
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
Hot charge-transfer excitons set the time limit for charge separation at donor/acceptor interfaces in organic photovoltaics Jailaubekov, Askat E.; Willard, Adam P.; Tritsch, John R. Nature Materials, Vol. 12, Issue 1 https://doi.org/10.1038/nmat3500	journal	December 2012
Charge Transfer State Versus Hot Exciton Dissociation in Polymer−Fullerene Blended Solar Cells Lee, Jiye; Vandewal, Koen; Yost, Shane R. Journal of the American Chemical Society, Vol. 132, Issue 34 https://doi.org/10.1021/ja1045742	journal	August 2010
Compositional and Electric Field Dependence of the Dissociation of Charge Transfer Excitons in Alternating Polyfluorene Copolymer/Fullerene Blends Veldman, Dirk; İpek, Özlem; Meskers, Stefan C. J. Journal of the American Chemical Society, Vol. 130, Issue 24 https://doi.org/10.1021/ja8012598	journal	May 2008
Ultrafast Long-Range Charge Separation in Organic Semiconductor Photovoltaic Diodes Gelinas, S.; Rao, A.; Kumar, A. Science, Vol. 343, Issue 6170 https://doi.org/10.1126/science.1246249	journal	December 2013
Hot exciton dissociation in polymer solar cells Grancini, G.; Maiuri, M.; Fazzi, D. Nature Materials, Vol. 12, Issue 1 https://doi.org/10.1038/nmat3502	journal	December 2012
Electric field assisted dissociation of charge transfer states as a mechanism of photocarrier production Braun, Charles L. The Journal of Chemical Physics, Vol. 80, Issue 9 https://doi.org/10.1063/1.447243	journal	May 1984
Barrierless Free Carrier Formation in an Organic Photovoltaic Material Measured with Ultrafast Vibrational Spectroscopy Pensack, Ryan D.; Asbury, John B. Journal of the American Chemical Society, Vol. 131, Issue 44 https://doi.org/10.1021/ja906293q	journal	November 2009
Unequal Partnership: Asymmetric Roles of Polymeric Donor and Fullerene Acceptor in Generating Free Charge Savoie, Brett M.; Rao, Akshay; Bakulin, Artem A. Journal of the American Chemical Society, Vol. 136, Issue 7 https://doi.org/10.1021/ja411859m	journal	February 2014
Mechanism of Mobile Charge Carrier Generation in Blends of Conjugated Polymers and Fullerenes: Significance of Charge Delocalization and Excess Free Energy Murthy, D. H. K.; Gao, M.; Vermeulen, M. J. W. The Journal of Physical Chemistry C, Vol. 116, Issue 16 https://doi.org/10.1021/jp3007014	journal	April 2012
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
What Controls the Rate of Ultrafast Charge Transfer and Charge Separation Efficiency in Organic Photovoltaic Blends Jakowetz, Andreas C.; Böhm, Marcus L.; Zhang, Jiangbin Journal of the American Chemical Society, Vol. 138, Issue 36 https://doi.org/10.1021/jacs.6b05131	journal	September 2016
Ultrafast Charge Separation in Organic Photovoltaics Enhanced by Charge Delocalization and Vibronically Hot Exciton Dissociation Tamura, Hiroyuki; Burghardt, Irene Journal of the American Chemical Society, Vol. 135, Issue 44 https://doi.org/10.1021/ja4093874	journal	October 2013
Influence of Acceptor Structure on Barriers to Charge Separation in Organic Photovoltaic Materials Pensack, Ryan D.; Guo, Changhe; Vakhshouri, Kiarash The Journal of Physical Chemistry C, Vol. 116, Issue 7 https://doi.org/10.1021/jp2083133	journal	January 2012
Photoinduced Electron Transfer in Self-Assembled Dimers of 3-Fold Symmetric Donor−Acceptor Molecules Based on Perylene-3,4:9,10-bis(dicarboximide) Rybtchinski, Boris; Sinks, Louise E.; Wasielewski, Michael R. The Journal of Physical Chemistry A, Vol. 108, Issue 37 https://doi.org/10.1021/jp048883u	journal	September 2004
Photoinitiated Charge Transport through π-Stacked Electron Conduits in Supramolecular Ordered Assemblies of Donor−Acceptor Triads Bullock, Joseph E.; Carmieli, Raanan; Mickley, Sarah M. Journal of the American Chemical Society, Vol. 131, Issue 33 https://doi.org/10.1021/ja903903q	journal	August 2009
On the road towards electroactive covalent organic frameworks Dogru, Mirjam; Bein, Thomas Chem. Commun., Vol. 50, Issue 42 https://doi.org/10.1039/C3CC46767H	journal	January 2014
Rationally synthesized two-dimensional polymers Colson, John W.; Dichtel, William R. Nature Chemistry, Vol. 5, Issue 6 https://doi.org/10.1038/nchem.1628	journal	May 2013
Charge Dynamics in A Donor-Acceptor Covalent Organic Framework with Periodically Ordered Bicontinuous Heterojunctions Jin, Shangbin; Ding, Xuesong; Feng, Xiao Angewandte Chemie International Edition, Vol. 52, Issue 7 https://doi.org/10.1002/anie.201209513	journal	January 2013
G-quadruplex organic frameworks Wu, Yi-Lin; Horwitz, Noah E.; Chen, Kan-Sheng Nature Chemistry, Vol. 9, Issue 5 https://doi.org/10.1038/nchem.2689	journal	December 2016
Stack Exchange Strategies for the Synthesis of Covalent Double-Channel Photosystems by Self-Organizing Surface-Initiated Polymerization Sakai, Naomi; Matile, Stefan Journal of the American Chemical Society, Vol. 133, Issue 46 https://doi.org/10.1021/ja207587x	journal	November 2011
Long-lived charge carrier generation in ordered films of a covalent perylenediimide–diketopyrrolopyrrole–perylenediimide molecule Hartnett, Patrick E.; Dyar, Scott M.; Margulies, Eric A. Chemical Science, Vol. 6, Issue 1 https://doi.org/10.1039/C4SC02551B	journal	January 2015
Top-down meets bottom-up: organized donor–acceptor heterojunctions for organic solar cells Wang, Mingfeng; Wudl, Fred Journal of Materials Chemistry, Vol. 22, Issue 46 https://doi.org/10.1039/c2jm33756h	journal	January 2012
Perylene Bisimide Dye Assemblies as Archetype Functional Supramolecular Materials Würthner, Frank; Saha-Möller, Chantu R.; Fimmel, Benjamin Chemical Reviews, Vol. 116, Issue 3 https://doi.org/10.1021/acs.chemrev.5b00188	journal	August 2015
Use of Side-Chain Incompatibility for Tailoring Long-Range p/n Heterojunctions: Photoconductive Nanofibers Formed by Self-Assembly of an Amphiphilic Donor-Acceptor Dyad Consisting of Oligothiophene and Perylenediimide Li, Wei-Shi; Saeki, Akinori; Yamamoto, Yohei Chemistry - An Asian Journal, Vol. 5, Issue 7 https://doi.org/10.1002/asia.201000111	journal	June 2010
Ultrafast Conformational Dynamics of Electron Transfer in ExBox ⁴⁺ ⊂Perylene Young, Ryan M.; Dyar, Scott M.; Barnes, Jonathan C. The Journal of Physical Chemistry A, Vol. 117, Issue 47 https://doi.org/10.1021/jp409883a	journal	November 2013
Scherrer grain-size analysis adapted to grazing-incidence scattering with area detectors Smilgies, Detlef-M. Journal of Applied Crystallography, Vol. 42, Issue 6 https://doi.org/10.1107/S0021889809040126	journal	October 2009
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
The integration of kinetic rate equations by matrix methods Berberan-Santos, M. N.; Martinho, J. M. G. Journal of Chemical Education, Vol. 67, Issue 5 https://doi.org/10.1021/ed067p375	journal	May 1990
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
The exciton model in molecular spectroscopy Kasha, M.; Rawls, H. R.; Ashraf El-Bayoumi, M. Pure and Applied Chemistry, Vol. 11, Issue 3-4 https://doi.org/10.1351/pac196511030371	journal	January 1965
Conjugated Porphyrin Ladders Anderson, Harry L. Inorganic Chemistry, Vol. 33, Issue 5 https://doi.org/10.1021/ic00083a022	journal	March 1994
Self-assembling hydrogel scaffolds for photocatalytic hydrogen production Weingarten, Adam S.; Kazantsev, Roman V.; Palmer, Liam C. Nature Chemistry, Vol. 6, Issue 11 https://doi.org/10.1038/nchem.2075	journal	October 2014
Carbon-hydrogen stretching modes and the structure of n-alkyl chains. 1. Long, disordered chains Snyder, R. G.; Strauss, H. L.; Elliger, C. A. The Journal of Physical Chemistry, Vol. 86, Issue 26 https://doi.org/10.1021/j100223a018	journal	December 1982
Fluorescence and FTIR Spectra Analysis of Trans-A2B2-Substituted Di- and Tetra-Phenyl Porphyrins Şen, Pınar; Hirel, Catherine; Andraud, Chantal Materials, Vol. 3, Issue 8 https://doi.org/10.3390/ma3084446	journal	August 2010
Excited Doublet States of Electrochemically Generated Aromatic Imide and Diimide Radical Anions Gosztola, David; Niemczyk, Mark P.; Svec, Walter The Journal of Physical Chemistry A, Vol. 104, Issue 28 https://doi.org/10.1021/jp000706f	journal	July 2000
Dark Carriers, Trapping, and Activation Control of Carrier Recombination in Neat P3HT and P3HT:PCBM Blends Ferguson, Andrew J.; Kopidakis, Nikos; Shaheen, Sean E. The Journal of Physical Chemistry C, Vol. 115, Issue 46 https://doi.org/10.1021/jp208014v	journal	October 2011
A strong regioregularity effect in self-organizing conjugated polymer films and high-efficiency polythiophene:fullerene solar cells Kim, Youngkyoo; Cook, Steffan; Tuladhar, Sachetan M. Nature Materials, Vol. 5, Issue 3 https://doi.org/10.1038/nmat1574	journal	February 2006
Transient optical studies of charge recombination dynamics in a polymer/fullerene composite at room temperature Montanari, Ivan; Nogueira, Ana F.; Nelson, Jenny Applied Physics Letters, Vol. 81, Issue 16 https://doi.org/10.1063/1.1512943	journal	October 2002
Time-resolved EPR spectroscopy of electron spin polarized ZnTPP triplets oriented in a liquid crystal Gonen, Oded; Levanon, Haim The Journal of Physical Chemistry, Vol. 89, Issue 9 https://doi.org/10.1021/j100255a017	journal	April 1985
Spin-Selective Charge Transport Pathways through p- Oligophenylene-Linked Donor−Bridge−Acceptor Molecules Scott, Amy M.; Miura, Tomoaki; Ricks, Annie Butler Journal of the American Chemical Society, Vol. 131, Issue 48 https://doi.org/10.1021/ja907625k	journal	December 2009
Spin-polarized electron paramagnetic resonance spectra of radical pairs in micelles: observation of electron spin-spin interactions Closs, Gerhard L.; Forbes, Malcolm D. E.; Norris, James R. The Journal of Physical Chemistry, Vol. 91, Issue 13 https://doi.org/10.1021/j100297a026	journal	June 1987
Photoinduced Charge Carrier Generation and Decay in Sequentially Deposited Polymer/Fullerene Layers: Bulk Heterojunction vs Planar Interface Nardes, Alexandre M.; Ayzner, Alexander L.; Hammond, Scott R. The Journal of Physical Chemistry C, Vol. 116, Issue 13 https://doi.org/10.1021/jp212390p	journal	March 2012
Bulk heterojunction solar cells with internal quantum efficiency approaching 100% Park, Sung Heum; Roy, Anshuman; Beaupré, Serge Nature Photonics, Vol. 3, Issue 5, p. 297-302 https://doi.org/10.1038/nphoton.2009.69	journal	April 2009
Conjugated Polymer Photovoltaic Cells Coakley, Kevin M.; McGehee, Michael D. Chemistry of Materials, Vol. 16, Issue 23, p. 4533-4542 https://doi.org/10.1021/cm049654n	journal	November 2004
Charge Generation and Recombination Dynamics in Poly(3-hexylthiophene)/Fullerene Blend Films with Different Regioregularities and Morphologies Guo, Jiamo; Ohkita, Hideo; Benten, Hiroaki Journal of the American Chemical Society, Vol. 132, Issue 17 https://doi.org/10.1021/ja100302p	journal	May 2010
An Optimal Driving Force for Converting Excitons into Free Carriers in Excitonic Solar Cells Coffey, David C.; Larson, Bryon W.; Hains, Alexander W. The Journal of Physical Chemistry C, Vol. 116, Issue 16 https://doi.org/10.1021/jp302275z	journal	April 2012
Reassessing the use of one-electron energetics in the design and characterization of organic photovoltaics Savoie, Brett M.; Jackson, Nicholas E.; Marks, Tobin J. Physical Chemistry Chemical Physics, Vol. 15, Issue 13 https://doi.org/10.1039/c3cp50438g	journal	January 2013
Multistep Photochemical Charge Separation in Rod-like Molecules Based on Aromatic Imides and Diimides Greenfield, Scott R.; Svec, Walter A.; Gosztola, David Journal of the American Chemical Society, Vol. 118, Issue 28 https://doi.org/10.1021/ja9600789	journal	January 1996
Coherent ultrafast charge transfer in an organic photovoltaic blend Falke, S. M.; Rozzi, C. A.; Brida, D. Science, Vol. 344, Issue 6187 https://doi.org/10.1126/science.1249771	journal	May 2014
Chemically Induced Dynamic Electron Polarization Study on the Mechanism of Exchange Interaction in Radical Ion Pairs Generated by Photoinduced Electron Transfer Reactions Kobori, Yasuhiro; Sekiguchi, Shinji; Akiyama, Kimio The Journal of Physical Chemistry A, Vol. 103, Issue 28 https://doi.org/10.1021/jp990359d	journal	July 1999
Mapping the Influence of Molecular Structure on Rates of Electron Transfer Using Direct Measurements of the Electron Spin−Spin Exchange Interaction Lukas, Aaron S.; Bushard, Patrick J.; Weiss, Emily A. Journal of the American Chemical Society, Vol. 125, Issue 13 https://doi.org/10.1021/ja029062a	journal	April 2003
Magnetic Field-Induced Switching of the Radical-Pair Intersystem Crossing Mechanism in a Donor−Bridge−Acceptor Molecule for Artificial Photosynthesis Colvin, Michael T.; Ricks, Annie Butler; Scott, Amy M. Journal of the American Chemical Society, Vol. 133, Issue 5 https://doi.org/10.1021/ja1094815	journal	February 2011
Chemically induced dynamic electron polarization. Examples; of S-T±1 polarization Trifunac, A. D.; Nelson, D. J.; Mottley, C. Journal of Magnetic Resonance (1969), Vol. 30, Issue 2 https://doi.org/10.1016/0022-2364(78)90100-2	journal	May 1978
Temperature-Independent Charge Carrier Photogeneration in P3HT−PCBM Blends with Different Morphology Grzegorczyk, Wojciech J.; Savenije, Tom J.; Dykstra, Tieneke E. The Journal of Physical Chemistry C, Vol. 114, Issue 11 https://doi.org/10.1021/jp9119364	journal	March 2010
Charge Carrier Formation in Polythiophene/Fullerene Blend Films Studied by Transient Absorption Spectroscopy Ohkita, Hideo; Cook, Steffan; Astuti, Yeni Journal of the American Chemical Society, Vol. 130, Issue 10 https://doi.org/10.1021/ja076568q	journal	March 2008
Photoinduced Electron Transfer Reactions in a Porphyrin−Viologen Complex: Observation of S ₂ to S ₁ Relaxation and Electron Transfer from the S ₂ State Andersson, Mikael; Davidsson, Jan; Hammarström, Leif The Journal of Physical Chemistry B, Vol. 103, Issue 16 https://doi.org/10.1021/jp9829795	journal	April 1999
Influence of Anion Delocalization on Electron Transfer in a Covalent Porphyrin Donor–Perylenediimide Dimer Acceptor System Hartnett, Patrick E.; Mauck, Catherine M.; Harris, Michelle A. Journal of the American Chemical Society, Vol. 139, Issue 2 https://doi.org/10.1021/jacs.6b10140	journal	January 2017
Molecular Packing Determines Charge Separation in a Liquid Crystalline Bisthiophene–Perylene Diimide Donor–Acceptor Material Polkehn, Matthias; Tamura, Hiroyuki; Eisenbrandt, Pierre The Journal of Physical Chemistry Letters, Vol. 7, Issue 7 https://doi.org/10.1021/acs.jpclett.6b00277	journal	March 2016

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