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

Journal Article · · Journal of Physical Chemistry. B
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)

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.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC00112704
OSTI ID:
1368672
Report Number(s):
BNL-114012-2017-JA; KC0403020
Journal Information:
Journal of Physical Chemistry. B, Vol. 121, Issue 7; ISSN 1520-6106
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

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Cited By (2)

Experimental and Theoretical Investigations of Different Diketopyrrolopyrrole-Based Polymers journal September 2018
Benchmark ab initio calculations on intermolecular structures and the exciton character of poly( p -phenylenevinylene) dimers journal January 2020