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Title: Side chain length affects backbone dynamics in poly(3-alkylthiophene)s

Abstract

Charge transport in conjugated polymers may be governed not only by the static microstructure but also fluctuations of backbone segments. Using molecular dynamics simulations, we predict the role of side chains in the backbone dynamics for regiorandom poly(3-alkylthiophene-2,5-diyl)s (P3ATs). Here, we show that the backbone of poly(3-dodecylthiophene-2-5-diyl) (P3DDT) moves faster than that of poly(3-hexylthiophene-2,5-diyl) (P3HT) as a result of the faster motion of the longer side chains. To verify our predictions, we investigated the structures and dynamics of regiorandom P3ATs with neutron scattering and solid state NMR. Measurements of spin-lattice relaxations (T1) using NMR support our prediction of faster motion for side chain atoms that are farther away from the backbone. Using small-angle neutron scattering (SANS), we confirmed that regiorandom P3ATs are amorphous at about 300K, although microphase separation between the side chains and backbones is apparent. Furthermore, Quasi-elastic neutron scattering (QENS) reveals that thiophene backbone motion is enhanced as the side chain length increases from hexyl to dodecyl. The faster motion of longer side chains leads to faster backbone dynamics, which in turn may affect charge transport for conjugated polymers.

Authors:
 [1];  [1];  [2];  [2];  [1];  [1];  [1];  [3];  [1];  [1]; ORCiD logo [4]
  1. Pennsylvania State Univ., University Park, PA (United States)
  2. Univ. of California, Davis, CA (United States)
  3. Univ. of California, Davis, CA (United States); Pennsylvania State Univ., University Park, PA (United States)
  4. Pennsylvania State Univ., University Park, PA (United States). Materials Research Inst.
Publication Date:
Research Org.:
Univ. of California, Davis, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1537607
Alternate Identifier(s):
OSTI ID: 1467533
Grant/Contract Number:  
SC0010419; DMR‐1629006
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Polymer Science. Part B, Polymer Physics
Additional Journal Information:
Journal Volume: 56; Journal Issue: 17; Journal ID: ISSN 0887-6266
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Polymer Science; Conjugated Polymers; Charge Transport; Side chain motion; Quasi Elastic Neutron Scattering; solid state NMR

Citation Formats

Zhan, Pengfei, Zhang, Wenlin, Jacobs, Ian E., Nisson, David M., Xie, Renxuan, Weissen, Albree R., Colby, Ralph H., Moulé, Adam J., Milner, Scott T., Maranas, Janna K., and Gomez, Enrique D. Side chain length affects backbone dynamics in poly(3-alkylthiophene)s. United States: N. p., 2018. Web. doi:10.1002/polb.24637.
Zhan, Pengfei, Zhang, Wenlin, Jacobs, Ian E., Nisson, David M., Xie, Renxuan, Weissen, Albree R., Colby, Ralph H., Moulé, Adam J., Milner, Scott T., Maranas, Janna K., & Gomez, Enrique D. Side chain length affects backbone dynamics in poly(3-alkylthiophene)s. United States. doi:10.1002/polb.24637.
Zhan, Pengfei, Zhang, Wenlin, Jacobs, Ian E., Nisson, David M., Xie, Renxuan, Weissen, Albree R., Colby, Ralph H., Moulé, Adam J., Milner, Scott T., Maranas, Janna K., and Gomez, Enrique D. Mon . "Side chain length affects backbone dynamics in poly(3-alkylthiophene)s". United States. doi:10.1002/polb.24637. https://www.osti.gov/servlets/purl/1537607.
@article{osti_1537607,
title = {Side chain length affects backbone dynamics in poly(3-alkylthiophene)s},
author = {Zhan, Pengfei and Zhang, Wenlin and Jacobs, Ian E. and Nisson, David M. and Xie, Renxuan and Weissen, Albree R. and Colby, Ralph H. and Moulé, Adam J. and Milner, Scott T. and Maranas, Janna K. and Gomez, Enrique D.},
abstractNote = {Charge transport in conjugated polymers may be governed not only by the static microstructure but also fluctuations of backbone segments. Using molecular dynamics simulations, we predict the role of side chains in the backbone dynamics for regiorandom poly(3-alkylthiophene-2,5-diyl)s (P3ATs). Here, we show that the backbone of poly(3-dodecylthiophene-2-5-diyl) (P3DDT) moves faster than that of poly(3-hexylthiophene-2,5-diyl) (P3HT) as a result of the faster motion of the longer side chains. To verify our predictions, we investigated the structures and dynamics of regiorandom P3ATs with neutron scattering and solid state NMR. Measurements of spin-lattice relaxations (T1) using NMR support our prediction of faster motion for side chain atoms that are farther away from the backbone. Using small-angle neutron scattering (SANS), we confirmed that regiorandom P3ATs are amorphous at about 300K, although microphase separation between the side chains and backbones is apparent. Furthermore, Quasi-elastic neutron scattering (QENS) reveals that thiophene backbone motion is enhanced as the side chain length increases from hexyl to dodecyl. The faster motion of longer side chains leads to faster backbone dynamics, which in turn may affect charge transport for conjugated polymers.},
doi = {10.1002/polb.24637},
journal = {Journal of Polymer Science. Part B, Polymer Physics},
number = 17,
volume = 56,
place = {United States},
year = {2018},
month = {8}
}

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