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Title: Influence of Nanostructure on the Exciton Dynamics of Multichromophore Donor–Acceptor Block Copolymers

Abstract

Here, we explore the synthesis and photophysics of nanostructured block copolymers that mimic light-harvesting complexes. We find that the combination of a polar and electron-rich boron dipyrromethene (BODIPY) block with a nonpolar electron-poor perylene diimide (PDI) block yields a polymer that self-assembles into ordered “nanoworms”. Numerical simulations are used to determine optimal compositions to achieve robust self-assembly. Photoluminescence spectroscopy is used to probe the rich exciton dynamics in these systems. Using controls, such as homopolymers and random copolymers, we analyze the mechanisms of the photoluminescence from these polymers. With this understanding it allows us to probe in detail the photophysics of the block copolymers, including the effects of their self-assembly into nanostructures on their excited-state properties. Similar to natural systems, ordered nanostructures result in properties that are starkly different than the properties of free polymers in solution, such as enhanced rates of electronic energy transfer and elimination of excitonic emission from disordered PDI trap states.

Authors:
 [1];  [2]; ORCiD logo [1];  [1];  [1]; ORCiD logo [3]; ORCiD logo [1]
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  1. Columbia Univ., New York, NY (United States). Dept. of Chemistry
  2. Columbia Univ., New York, NY (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Energy Frontier Research Centers (EFRC) (United States). Re-Defining Photovoltaic Efficiency Through Molecule Scale Control (RPEMSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1394757
Report Number(s):
BNL-114328-2017-JA
Journal ID: ISSN 1936-0851; KC0403020
Grant/Contract Number:  
SC0012704; SC0001085; DMR-1408259
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 11; Journal Issue: 5; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; excitonics; nanotechnology; organic electronics; photophysics; polymer chemistry; self-assembly

Citation Formats

Xia, Jianlong, Busby, Erik, Sanders, Samuel N., Tung, Clarion, Cacciuto, Angelo, Sfeir, Matthew Y., and Campos, Luis M. Influence of Nanostructure on the Exciton Dynamics of Multichromophore Donor–Acceptor Block Copolymers. United States: N. p., 2017. Web. doi:10.1021/acsnano.7b00056.
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Xia, Jianlong, Busby, Erik, Sanders, Samuel N., Tung, Clarion, Cacciuto, Angelo, Sfeir, Matthew Y., & Campos, Luis M. Influence of Nanostructure on the Exciton Dynamics of Multichromophore Donor–Acceptor Block Copolymers. United States. https://doi.org/10.1021/acsnano.7b00056
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Xia, Jianlong, Busby, Erik, Sanders, Samuel N., Tung, Clarion, Cacciuto, Angelo, Sfeir, Matthew Y., and Campos, Luis M. Mon . "Influence of Nanostructure on the Exciton Dynamics of Multichromophore Donor–Acceptor Block Copolymers". United States. https://doi.org/10.1021/acsnano.7b00056. https://www.osti.gov/servlets/purl/1394757.
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@article{osti_1394757,
title = {Influence of Nanostructure on the Exciton Dynamics of Multichromophore Donor–Acceptor Block Copolymers},
author = {Xia, Jianlong and Busby, Erik and Sanders, Samuel N. and Tung, Clarion and Cacciuto, Angelo and Sfeir, Matthew Y. and Campos, Luis M.},
abstractNote = {Here, we explore the synthesis and photophysics of nanostructured block copolymers that mimic light-harvesting complexes. We find that the combination of a polar and electron-rich boron dipyrromethene (BODIPY) block with a nonpolar electron-poor perylene diimide (PDI) block yields a polymer that self-assembles into ordered “nanoworms”. Numerical simulations are used to determine optimal compositions to achieve robust self-assembly. Photoluminescence spectroscopy is used to probe the rich exciton dynamics in these systems. Using controls, such as homopolymers and random copolymers, we analyze the mechanisms of the photoluminescence from these polymers. With this understanding it allows us to probe in detail the photophysics of the block copolymers, including the effects of their self-assembly into nanostructures on their excited-state properties. Similar to natural systems, ordered nanostructures result in properties that are starkly different than the properties of free polymers in solution, such as enhanced rates of electronic energy transfer and elimination of excitonic emission from disordered PDI trap states.},
doi = {10.1021/acsnano.7b00056},
journal = {ACS Nano},
number = 5,
volume = 11,
place = {United States},
year = {Mon Mar 27 00:00:00 EDT 2017},
month = {Mon Mar 27 00:00:00 EDT 2017}
}
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https://doi.org/10.1021/acsnano.7b00056
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Works referenced in this record:

Lessons from nature about solar light harvesting
journal, September 2011

  • Scholes, Gregory D.; Fleming, Graham R.; Olaya-Castro, Alexandra
  • Nature Chemistry, Vol. 3, Issue 10
  • DOI: 10.1038/nchem.1145

Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature
journal, February 2010

  • Collini, Elisabetta; Wong, Cathy Y.; Wilk, Krystyna E.
  • Nature, Vol. 463, Issue 7281
  • DOI: 10.1038/nature08811

On the Mechanism of Light Harvesting in Photosynthetic Purple Bacteria:  B800 to B850 Energy Transfer
journal, March 2000

  • Scholes, Gregory D.; Fleming, Graham R.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 8
  • DOI: 10.1021/jp993435l

Conjugated Block Copolymer Photovoltaics with near 3% Efficiency through Microphase Separation
journal, May 2013

  • Guo, Changhe; Lin, Yen-Hao; Witman, Matthew D.
  • Nano Letters, Vol. 13, Issue 6
  • DOI: 10.1021/nl401420s

Synthesis and crystallinity of all-conjugated poly(3-hexylthiophene) block copolymers
journal, January 2013

  • Lin, Yen-Hao; Smith, Kendall A.; Kempf, Chloe N.
  • Polym. Chem., Vol. 4, Issue 2
  • DOI: 10.1039/C2PY20830J

Extended Charge Carrier Lifetimes in Hierarchical Donor–Acceptor Supramolecular Polymer Films
journal, August 2015

  • Guzman, Carmen X.; Calderon, Rafael M. Krick; Li, Zhong
  • The Journal of Physical Chemistry C, Vol. 119, Issue 34
  • DOI: 10.1021/acs.jpcc.5b03713

Cooperatively Assembling Donor–Acceptor Superstructures Direct Energy Into an Emergent Charge Separated State
journal, May 2014

  • Ley, David; Guzman, Carmen X.; Adolfsson, Karin H.
  • Journal of the American Chemical Society, Vol. 136, Issue 22
  • DOI: 10.1021/ja5015053

Formation of a long-lived charge-separated state of a zinc phthalocyanine-perylenediimide dyad by complexation with magnesium ion
journal, January 2005

  • Fukuzumi, Shunichi; Ohkubo, Kei; Ortiz, Javier
  • Chemical Communications, Issue 30
  • DOI: 10.1039/b506412k

Utilizing redox-chemistry to elucidate the nature of exciton transitions in supramolecular dye nanotubes
journal, July 2012

  • Eisele, D. M.; Cone, C. W.; Bloemsma, E. A.
  • Nature Chemistry, Vol. 4, Issue 8
  • DOI: 10.1038/nchem.1380

Vibronic and Vibrational Coherences in Two-Dimensional Electronic Spectra of Supramolecular J-Aggregates
journal, March 2013

  • Milota, Franz; Prokhorenko, Valentyn I.; Mancal, Tomas
  • The Journal of Physical Chemistry A, Vol. 117, Issue 29
  • DOI: 10.1021/jp3119605

Synthesis and Self-Assembly of Donor–Acceptor–Donor Based Oligothiophenes and Their Optoelectronic Properties
journal, July 2011

  • Siram, Raja Bhaskar Kanth; Tandy, Kristen; Horecha, Marta
  • The Journal of Physical Chemistry C, Vol. 115, Issue 29
  • DOI: 10.1021/jp204271c

Functional polymers by atom transfer radical polymerization
journal, April 2001

  • Coessens, Veerle; Pintauer, Tomislav; Matyjaszewski, Krzysztof
  • Progress in Polymer Science, Vol. 26, Issue 3
  • DOI: 10.1016/S0079-6700(01)00003-X

Atom Transfer Radical Polymerization
journal, September 2001

  • Matyjaszewski, Krzysztof; Xia, Jianhui
  • Chemical Reviews, Vol. 101, Issue 9
  • DOI: 10.1021/cr940534g

Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes
journal, May 1995

  • Wang, Jin-Shan; Matyjaszewski, Krzysztof
  • Journal of the American Chemical Society, Vol. 117, Issue 20
  • DOI: 10.1021/ja00125a035

The Convergence of Synthetic Organic and Polymer Chemistries
journal, August 2005

Controlled Synthesis of Polymer Brushes by “Living” Free Radical Polymerization Techniques
journal, March 1999

  • Husseman, Marc; Malmström, Eva E.; McNamara, Molly
  • Macromolecules, Vol. 32, Issue 5
  • DOI: 10.1021/ma981290v

Multidimensional hierarchical self-assembly of amphiphilic cylindrical block comicelles
journal, March 2015

Complex and hierarchical micelle architectures from diblock copolymers using living, crystallization-driven polymerizations
journal, January 2009

  • Gädt, Torben; Ieong, Nga Sze; Cambridge, Graeme
  • Nature Materials, Vol. 8, Issue 2
  • DOI: 10.1038/nmat2356

Photoinduced Electron Transfer in Hydrogen-Bonded Oligo( p -phenylene vinylene)−Perylene Bisimide Chiral Assemblies
journal, July 2002

  • Schenning, Albertus P. H. J.; v. Herrikhuyzen, Jeroen; Jonkheijm, Pascal
  • Journal of the American Chemical Society, Vol. 124, Issue 35
  • DOI: 10.1021/ja020378s

About Supramolecular Assemblies of π-Conjugated Systems
journal, April 2005

  • Hoeben, Freek J. M.; Jonkheijm, Pascal; Meijer, E. W.
  • Chemical Reviews, Vol. 105, Issue 4
  • DOI: 10.1021/cr030070z

Growth of Polythiophene/Perylene Tetracarboxydiimide Donor/Acceptor Shish-Kebab Nanostructures by Coupled Crystal Modification
journal, November 2012

  • Bu, Laju; Pentzer, Emily; Bokel, Felicia A.
  • ACS Nano, Vol. 6, Issue 12
  • DOI: 10.1021/nn3043836

Block copolymer strategies for solar cell technology
journal, June 2011

  • Topham, Paul D.; Parnell, Andrew J.; Hiorns, Roger C.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 49, Issue 16
  • DOI: 10.1002/polb.22302

Monoliths of Semiconducting Block Copolymers by Magnetic Alignment
journal, May 2013

  • Tran, Helen; Gopinadhan, Manesh; Majewski, Pawel W.
  • ACS Nano, Vol. 7, Issue 6
  • DOI: 10.1021/nn401725a

Effects of functional groups at perylene diimide derivatives on organic photovoltaic device application
journal, January 2006

  • Shin, Won Suk; Jeong, Hwan-Hee; Kim, Mi-Kyoung
  • J. Mater. Chem., Vol. 16, Issue 4
  • DOI: 10.1039/B512983D

Self-Assembly Strategies for Integrating Light Harvesting and Charge Separation in Artificial Photosynthetic Systems
journal, December 2009

  • Wasielewski, Michael R.
  • Accounts of Chemical Research, Vol. 42, Issue 12
  • DOI: 10.1021/ar9001735

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995

Preparation of non-spherical particles from amphiphilic block copolymers
journal, October 2015

  • Kempe, Kristian; Wylie, Ross A.; Dimitriou, Michael D.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 54, Issue 6
  • DOI: 10.1002/pola.27927

De Novo Design of Bioactive Protein-Resembling Nanospheres via Dendrimer-Templated Peptide Amphiphile Assembly
journal, September 2011

  • Lin, Brian F.; Marullo, Rachel S.; Robb, Maxwell J.
  • Nano Letters, Vol. 11, Issue 9
  • DOI: 10.1021/nl202220q

Tuning the assembly of amphiphilic block copolymers through instabilities of solvent/water interfaces in the presence of aqueous surfactants
journal, January 2009

  • Zhu, Jintao; Ferrer, Nangelie; Hayward, Ryan C.
  • Soft Matter, Vol. 5, Issue 12
  • DOI: 10.1039/b818065b

BODIPY Dyes and Their Derivatives:  Syntheses and Spectroscopic Properties
journal, November 2007

  • Loudet, Aurore; Burgess, Kevin
  • Chemical Reviews, Vol. 107, Issue 11
  • DOI: 10.1021/cr078381n

Direct Observation of Ultrafast Excimer Formation in Covalent Perylenediimide Dimers Using Near-Infrared Transient Absorption Spectroscopy
journal, July 2014

  • Brown, Kristen E.; Salamant, Walter A.; Shoer, Leah E.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 15
  • DOI: 10.1021/jz5011797

Excimer formation in cofacial and slip-stacked perylene-3,4:9,10-bis(dicarboximide) dimers on a redox-inactive triptycene scaffold
journal, January 2014

  • Margulies, Eric A.; Shoer, Leah E.; Eaton, Samuel W.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 43
  • DOI: 10.1039/C4CP03107E

Energy and Electron Transfer of One-Dimensional Nanomaterials of Perylenediimides
journal, January 2013

  • Supur, Mustafa; Fukuzumi, Shunichi
  • ECS Journal of Solid State Science and Technology, Vol. 2, Issue 10
  • DOI: 10.1149/2.009310jss

Quantitative Intramolecular Singlet Fission in Bipentacenes
journal, July 2015

  • Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B.
  • Journal of the American Chemical Society, Vol. 137, Issue 28
  • DOI: 10.1021/jacs.5b04986
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    Works referencing / citing this record:

    Recent advances in amphiphilic block copolymer templated mesoporous metal-based materials: assembly engineering and applications
    journal, January 2020

    • Zou, Yidong; Zhou, Xinran; Ma, Junhao
    • Chemical Society Reviews, Vol. 49, Issue 4
    • DOI: 10.1039/c9cs00334g
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