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Title: Conformational Order in Aggregates of Conjugated Polymers

Abstract

With the abundant variety and increasing chemical complexity of conjugated poly-friers proliferating the field of organic semiconductors, it has become increasingly important to correlate the polymer molecular structure with its mesoscale conformational and morphological attributes. For instance, it is unknown which combinations of chemical moieties and periodicities predictably produce mesoscale ordering. Interestingly) not all ordered morphologies result in efficient devices. In this work we have parametrized accurate classical force-fields and used these to compute the conformational and aggregation characteristics of single strands of common conjugated polymers. Molecular dynamics trajectories are shown to reproduce experimentally observed polymeric ordering, concluding that efficient organic photovoltaic devices span a range of polymer conformational classes, and suggesting that the solution-phase morphologies have far-reaching effects. Encouragingly, these simulations indicate that despite the wide-range of conformational classes present in successful devices, local molecular ordering, and not long-range crystallinity, appears to be the necessary requirement for efficient devices. Finally, we examine what makes a "good" solvent for conjugated polymers, concluding that dispersive pi-electron solvent-polymer interactions, and not the electrostatic potential of the backbone interacting with the solvent, are what primarily determine a polymer's solubility in a particular solvent, and consequently its morphological characteristics.

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [1]
  1. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
  2. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1392402
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 137; Journal Issue: 19; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

Jackson, Nicholas E., Kohlstedt, Kevin L., Savoie, Brett M., Olvera de la Cruz, Monica, Schatz, George C., Chen, Lin X., and Ratner, Mark A. Conformational Order in Aggregates of Conjugated Polymers. United States: N. p., 2015. Web. doi:10.1021/jacs.5b00493.
Jackson, Nicholas E., Kohlstedt, Kevin L., Savoie, Brett M., Olvera de la Cruz, Monica, Schatz, George C., Chen, Lin X., & Ratner, Mark A. Conformational Order in Aggregates of Conjugated Polymers. United States. doi:10.1021/jacs.5b00493.
Jackson, Nicholas E., Kohlstedt, Kevin L., Savoie, Brett M., Olvera de la Cruz, Monica, Schatz, George C., Chen, Lin X., and Ratner, Mark A. Wed . "Conformational Order in Aggregates of Conjugated Polymers". United States. doi:10.1021/jacs.5b00493.
@article{osti_1392402,
title = {Conformational Order in Aggregates of Conjugated Polymers},
author = {Jackson, Nicholas E. and Kohlstedt, Kevin L. and Savoie, Brett M. and Olvera de la Cruz, Monica and Schatz, George C. and Chen, Lin X. and Ratner, Mark A.},
abstractNote = {With the abundant variety and increasing chemical complexity of conjugated poly-friers proliferating the field of organic semiconductors, it has become increasingly important to correlate the polymer molecular structure with its mesoscale conformational and morphological attributes. For instance, it is unknown which combinations of chemical moieties and periodicities predictably produce mesoscale ordering. Interestingly) not all ordered morphologies result in efficient devices. In this work we have parametrized accurate classical force-fields and used these to compute the conformational and aggregation characteristics of single strands of common conjugated polymers. Molecular dynamics trajectories are shown to reproduce experimentally observed polymeric ordering, concluding that efficient organic photovoltaic devices span a range of polymer conformational classes, and suggesting that the solution-phase morphologies have far-reaching effects. Encouragingly, these simulations indicate that despite the wide-range of conformational classes present in successful devices, local molecular ordering, and not long-range crystallinity, appears to be the necessary requirement for efficient devices. Finally, we examine what makes a "good" solvent for conjugated polymers, concluding that dispersive pi-electron solvent-polymer interactions, and not the electrostatic potential of the backbone interacting with the solvent, are what primarily determine a polymer's solubility in a particular solvent, and consequently its morphological characteristics.},
doi = {10.1021/jacs.5b00493},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 19,
volume = 137,
place = {United States},
year = {2015},
month = {5}
}