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Title: Exciton–exciton annihilation as a probe of interchain interactions in PPV–oligomer aggregates

One measure of exciton mobility in an aggregate is the efficiency of exciton–exciton annihilation (EEA). Both exciton mobilities and EEA are enhanced for aggregate morphologies in which the distances between chromophores and their relative orientations are favorable for Förster energy transfer. Here this principle is applied to gauge the strength of interchain interactions in aggregates of two substituted PPV oligomers of 7 (OPPV7) and 13 (OPPV13) phenylene rings. These are models of the semiconducting conjugated polymer MEH–PPV. The aggregates were formed by adding a poor solvent (methanol or water) to the oligomers dissolved in a good solvent. Aggregates formed from the longer-chain oligomer and/or by addition of the more polar solvent showed the largest contribution of EEA in their emission decay dynamics. This was found to correlate with the degree to which the steady-state emission spectrum of the monomer is altered by aggregation. Furthermore, the wavelength dependence of the EEA signal was also shown to be useful in differentiating emission features due to monomeric and aggregated chains when their spectra overlap significantly.
Authors:
ORCiD logo [1] ; ORCiD logo [2] ;  [3] ; ORCiD logo [4]
  1. Carnegie Mellon Univ., Pittsburgh, PA (United States)
  2. Carnegie Mellon Univ., Pittsburgh, PA (United States); New Mexico Tech, Socorro, NM (United States)
  3. Zernike Institute of Advanced Materials, AG Groningen (The Netherlands)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Report Number(s):
BNL-114012-2017-JA
Journal ID: ISSN 1520-6106; KC0403020
Grant/Contract Number:
SC00112704
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 121; Journal Issue: 7; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Research Org:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Center for Functional Nanomaterials
OSTI Identifier:
1368672

Peteanu, Linda A., Chowdhury, Sanchari, Wildeman, Jurjen, and Sfeir, Matthew Y.. Exciton–exciton annihilation as a probe of interchain interactions in PPV–oligomer aggregates. United States: N. p., Web. doi:10.1021/acs.jpcb.6b11250.
Peteanu, Linda A., Chowdhury, Sanchari, Wildeman, Jurjen, & Sfeir, Matthew Y.. Exciton–exciton annihilation as a probe of interchain interactions in PPV–oligomer aggregates. United States. doi:10.1021/acs.jpcb.6b11250.
Peteanu, Linda A., Chowdhury, Sanchari, Wildeman, Jurjen, and Sfeir, Matthew Y.. 2017. "Exciton–exciton annihilation as a probe of interchain interactions in PPV–oligomer aggregates". United States. doi:10.1021/acs.jpcb.6b11250. https://www.osti.gov/servlets/purl/1368672.
@article{osti_1368672,
title = {Exciton–exciton annihilation as a probe of interchain interactions in PPV–oligomer aggregates},
author = {Peteanu, Linda A. and Chowdhury, Sanchari and Wildeman, Jurjen and Sfeir, Matthew Y.},
abstractNote = {One measure of exciton mobility in an aggregate is the efficiency of exciton–exciton annihilation (EEA). Both exciton mobilities and EEA are enhanced for aggregate morphologies in which the distances between chromophores and their relative orientations are favorable for Förster energy transfer. Here this principle is applied to gauge the strength of interchain interactions in aggregates of two substituted PPV oligomers of 7 (OPPV7) and 13 (OPPV13) phenylene rings. These are models of the semiconducting conjugated polymer MEH–PPV. The aggregates were formed by adding a poor solvent (methanol or water) to the oligomers dissolved in a good solvent. Aggregates formed from the longer-chain oligomer and/or by addition of the more polar solvent showed the largest contribution of EEA in their emission decay dynamics. This was found to correlate with the degree to which the steady-state emission spectrum of the monomer is altered by aggregation. Furthermore, the wavelength dependence of the EEA signal was also shown to be useful in differentiating emission features due to monomeric and aggregated chains when their spectra overlap significantly.},
doi = {10.1021/acs.jpcb.6b11250},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 7,
volume = 121,
place = {United States},
year = {2017},
month = {1}
}