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

Journal Article · · ACS Nano
 [1];  [2]; ORCiD logo [1];  [1];  [1]; ORCiD logo [3]; ORCiD logo [1]
  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
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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.

Research Organization:
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 Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
SC0012704; SC0001085; DMR-1408259
OSTI ID:
1394757
Report Number(s):
BNL-114328-2017-JA; KC0403020
Journal Information:
ACS Nano, Vol. 11, Issue 5; ISSN 1936-0851
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

References (35)

Lessons from nature about solar light harvesting journal September 2011
Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature journal February 2010
On the Mechanism of Light Harvesting in Photosynthetic Purple Bacteria:  B800 to B850 Energy Transfer journal March 2000
Conjugated Block Copolymer Photovoltaics with near 3% Efficiency through Microphase Separation journal May 2013
Synthesis and crystallinity of all-conjugated poly(3-hexylthiophene) block copolymers journal January 2013
Polythiophene- block -polyfluorene and Polythiophene- block -poly(fluorene- co -benzothiadiazole): Insights into the Self-Assembly of All-Conjugated Block Copolymers journal February 2011
Extended Charge Carrier Lifetimes in Hierarchical Donor–Acceptor Supramolecular Polymer Films journal August 2015
Cooperatively Assembling Donor–Acceptor Superstructures Direct Energy Into an Emergent Charge Separated State journal May 2014
Formation of a long-lived charge-separated state of a zinc phthalocyanine-perylenediimide dyad by complexation with magnesium ion journal January 2005
Utilizing redox-chemistry to elucidate the nature of exciton transitions in supramolecular dye nanotubes journal July 2012
Vibronic and Vibrational Coherences in Two-Dimensional Electronic Spectra of Supramolecular J-Aggregates journal March 2013
Synthesis and Self-Assembly of Donor–Acceptor–Donor Based Oligothiophenes and Their Optoelectronic Properties journal July 2011
Functional polymers by atom transfer radical polymerization journal April 2001
Atom Transfer Radical Polymerization journal September 2001
Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes journal May 1995
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
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
Photoinduced Electron Transfer in Hydrogen-Bonded Oligo( p -phenylene vinylene)−Perylene Bisimide Chiral Assemblies
  • Schenning, Albertus P. H. J.; v. Herrikhuyzen, Jeroen; Jonkheijm, Pascal
  • Journal of the American Chemical Society, Vol. 124, Issue 35 https://doi.org/10.1021/ja020378s
journal July 2002
About Supramolecular Assemblies of π-Conjugated Systems journal April 2005
Growth of Polythiophene/Perylene Tetracarboxydiimide Donor/Acceptor Shish-Kebab Nanostructures by Coupled Crystal Modification journal November 2012
Block copolymer strategies for solar cell technology journal June 2011
Monoliths of Semiconducting Block Copolymers by Magnetic Alignment journal May 2013
Effects of functional groups at perylene diimide derivatives on organic photovoltaic device application journal January 2006
Self-Assembly Strategies for Integrating Light Harvesting and Charge Separation in Artificial Photosynthetic Systems journal December 2009
Fast Parallel Algorithms for Short-Range Molecular Dynamics journal March 1995
Preparation of non-spherical particles from amphiphilic block copolymers journal October 2015
De Novo Design of Bioactive Protein-Resembling Nanospheres via Dendrimer-Templated Peptide Amphiphile Assembly journal September 2011
Tuning the assembly of amphiphilic block copolymers through instabilities of solvent/water interfaces in the presence of aqueous surfactants journal January 2009
BODIPY Dyes and Their Derivatives:  Syntheses and Spectroscopic Properties journal November 2007
Direct Observation of Ultrafast Excimer Formation in Covalent Perylenediimide Dimers Using Near-Infrared Transient Absorption Spectroscopy journal July 2014
Excimer formation in cofacial and slip-stacked perylene-3,4:9,10-bis(dicarboximide) dimers on a redox-inactive triptycene scaffold journal January 2014
Energy and Electron Transfer of One-Dimensional Nanomaterials of Perylenediimides journal January 2013
Quantitative Intramolecular Singlet Fission in Bipentacenes journal July 2015

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

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
excitonics
nanotechnology
organic electronics
photophysics
polymer chemistry
self-assembly