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Title: Self-Assembly Behavior of an Oligothiophene-Based Conjugated Liquid Crystal and Its Implication for Ionic Conductivity Characteristics

Abstract

Here, a joint experimental and computational study on the synthesis, selfassembly and ionic conduction characteristics of a new conjugated liquid crystal quaterthiophene/poly(ethylene oxide) (PEO4) consisting of terminal tetraethyleneglycol monomethyl ether groups on both ends of a quaterthiophene core. In agreement with molecular dynamic simulations, temperature-dependent grazing-incidence wide angle X-ray scattering and X-ray diffraction indicate that the molecule spontaneously forms a smectic phase at ambient temperature as characterized both in bulk and thin film configurations. Significantly, this smectic phase is maintained upon blending with bis(trifluoro-methanesulfonyl)imide (LiTFSI) as ion source at a concentration ratio up to r = [Li+]/[EO] = 0.05. Nanosegregation between oligothiophene and PEO moieties and π-π stacking of thiophene rings led to the formation of efficient 2D pathways for ion transport, resulting in thin film in-plane ionic conductivity as high as 5.2 x 10-4 S/cm-1 at 70°C and r = 0.05 as measured by electrochemical impedance spectroscopy (EIS). Upon heating the samples above a transition temperature around 95 °C, a less ordered phase forms associated with a pronounced drop in ionic conductivity. Finally, upon cooling, partial and local reordering of the conducting smectic domains leads to an ionic conductivity decrease compared to the as-cast state.

Authors:
 [1];  [2];  [1];  [1];  [3];  [4]; ORCiD logo [1];  [4]; ORCiD logo [1]
  1. Cornell Univ., Ithaca, NY (United States)
  2. Univ. of Chicago, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1491829
Alternate Identifier(s):
OSTI ID: 1482268
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 2; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ionic conductivity; liquid crystal; oligothiophene; self-assembly; π-π interactions

Citation Formats

Liu, Ziwei, Dong, Ban Xuan, Misra, Mayank, Sun, Yangyang, Strzalka, Joseph, Patel, Shrayesh N., Escobedo, Fernando A., Nealey, Paul F., and Ober, Christopher K. Self-Assembly Behavior of an Oligothiophene-Based Conjugated Liquid Crystal and Its Implication for Ionic Conductivity Characteristics. United States: N. p., 2018. Web. doi:10.1002/adfm.201805220.
Liu, Ziwei, Dong, Ban Xuan, Misra, Mayank, Sun, Yangyang, Strzalka, Joseph, Patel, Shrayesh N., Escobedo, Fernando A., Nealey, Paul F., & Ober, Christopher K. Self-Assembly Behavior of an Oligothiophene-Based Conjugated Liquid Crystal and Its Implication for Ionic Conductivity Characteristics. United States. doi:10.1002/adfm.201805220.
Liu, Ziwei, Dong, Ban Xuan, Misra, Mayank, Sun, Yangyang, Strzalka, Joseph, Patel, Shrayesh N., Escobedo, Fernando A., Nealey, Paul F., and Ober, Christopher K. Wed . "Self-Assembly Behavior of an Oligothiophene-Based Conjugated Liquid Crystal and Its Implication for Ionic Conductivity Characteristics". United States. doi:10.1002/adfm.201805220. https://www.osti.gov/servlets/purl/1491829.
@article{osti_1491829,
title = {Self-Assembly Behavior of an Oligothiophene-Based Conjugated Liquid Crystal and Its Implication for Ionic Conductivity Characteristics},
author = {Liu, Ziwei and Dong, Ban Xuan and Misra, Mayank and Sun, Yangyang and Strzalka, Joseph and Patel, Shrayesh N. and Escobedo, Fernando A. and Nealey, Paul F. and Ober, Christopher K.},
abstractNote = {Here, a joint experimental and computational study on the synthesis, selfassembly and ionic conduction characteristics of a new conjugated liquid crystal quaterthiophene/poly(ethylene oxide) (PEO4) consisting of terminal tetraethyleneglycol monomethyl ether groups on both ends of a quaterthiophene core. In agreement with molecular dynamic simulations, temperature-dependent grazing-incidence wide angle X-ray scattering and X-ray diffraction indicate that the molecule spontaneously forms a smectic phase at ambient temperature as characterized both in bulk and thin film configurations. Significantly, this smectic phase is maintained upon blending with bis(trifluoro-methanesulfonyl)imide (LiTFSI) as ion source at a concentration ratio up to r = [Li+]/[EO] = 0.05. Nanosegregation between oligothiophene and PEO moieties and π-π stacking of thiophene rings led to the formation of efficient 2D pathways for ion transport, resulting in thin film in-plane ionic conductivity as high as 5.2 x 10-4 S/cm-1 at 70°C and r = 0.05 as measured by electrochemical impedance spectroscopy (EIS). Upon heating the samples above a transition temperature around 95 °C, a less ordered phase forms associated with a pronounced drop in ionic conductivity. Finally, upon cooling, partial and local reordering of the conducting smectic domains leads to an ionic conductivity decrease compared to the as-cast state.},
doi = {10.1002/adfm.201805220},
journal = {Advanced Functional Materials},
number = 2,
volume = 29,
place = {United States},
year = {2018},
month = {11}
}

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