Effects of tacticity and chiral center-to-dipole distance on mesogen-free liquid crystalline self-assembly of sulfonyl-containing comb-like polymers
Abstract
In this report, new approaches were implemented to achieve novel ferroelectric liquid crystalline self-assembly in mesogen-free comb-like isotactic polyoxypropylenes (iPOPs) bearing mono- or di-sulfonyl groups, which have potential to exhibit high spontaneous polarization for applications in advanced electronic devices. iPOPs with n-alkylsulfonylpentylthioether side chains (iPOP-SC5SO2Cn, where Cn is the alkyl tail with n being either 12 or 8) were prepared via a post-polymerization substitution reaction from isotactic poly[(R)-(–)-epichlorohydrin]. Here, the effects of main-chain tacticity, chiral center-to-dipole distance, number of sulfonyl dipoles per side chain, and n-alkyl tail length on the liquid crystalline self-assembly behavior were investigated by comparing iPOPs with their atactic counterparts. First, when the sulfonyl dipole was placed far away from the chiral center in iPOP-SC5SO2Cn compared with our previously reported isotactic polyethers with n-alkylsulfonyl side chains (iPOP-SO2Cn), the dipole–dipole interactions among the side chains decreased, which led to more liquid crystalline phases. Smectic E (SmE) and A (SmA) phases were observed after crystal melting; however, the main-chain chiral center was found to have an insignificant effect on the liquid crystalline assembly when compared to the atactic samples. Second, the longer Cn tails increased the transition temperatures as a result of stronger van der Waals interactions. Third, aftermore »
- Authors:
-
[2];
[1]
- Univ. of Tennessee, Knoxville, TN (United States)
- Case Western Reserve Univ., Cleveland, OH (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States); Case Western Reserve Univ., Cleveland, OH (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1633601
- Alternate Identifier(s):
- OSTI ID: 1608500; OSTI ID: 1899875
- Report Number(s):
- BNL-216041-2020-JAAM
Journal ID: ISSN 1759-9954; PCOHC2
- Grant/Contract Number:
- SC0012704; SC0018075
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Polymer Chemistry
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 17; Journal ID: ISSN 1759-9954
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Mesogen-free; comb-like polymers; chirality effect; sulfonyl dipole; polyoxypropylenes
Citation Formats
Bohannon, Caleb A., Kwok, Man-Hin, Li, Ruipeng, Zhu, Lei, and Zhao, Bin. Effects of tacticity and chiral center-to-dipole distance on mesogen-free liquid crystalline self-assembly of sulfonyl-containing comb-like polymers. United States: N. p., 2020.
Web. doi:10.1039/D0PY00199F.
Bohannon, Caleb A., Kwok, Man-Hin, Li, Ruipeng, Zhu, Lei, & Zhao, Bin. Effects of tacticity and chiral center-to-dipole distance on mesogen-free liquid crystalline self-assembly of sulfonyl-containing comb-like polymers. United States. https://doi.org/10.1039/D0PY00199F
Bohannon, Caleb A., Kwok, Man-Hin, Li, Ruipeng, Zhu, Lei, and Zhao, Bin. Mon .
"Effects of tacticity and chiral center-to-dipole distance on mesogen-free liquid crystalline self-assembly of sulfonyl-containing comb-like polymers". United States. https://doi.org/10.1039/D0PY00199F. https://www.osti.gov/servlets/purl/1633601.
@article{osti_1633601,
title = {Effects of tacticity and chiral center-to-dipole distance on mesogen-free liquid crystalline self-assembly of sulfonyl-containing comb-like polymers},
author = {Bohannon, Caleb A. and Kwok, Man-Hin and Li, Ruipeng and Zhu, Lei and Zhao, Bin},
abstractNote = {In this report, new approaches were implemented to achieve novel ferroelectric liquid crystalline self-assembly in mesogen-free comb-like isotactic polyoxypropylenes (iPOPs) bearing mono- or di-sulfonyl groups, which have potential to exhibit high spontaneous polarization for applications in advanced electronic devices. iPOPs with n-alkylsulfonylpentylthioether side chains (iPOP-SC5SO2Cn, where Cn is the alkyl tail with n being either 12 or 8) were prepared via a post-polymerization substitution reaction from isotactic poly[(R)-(–)-epichlorohydrin]. Here, the effects of main-chain tacticity, chiral center-to-dipole distance, number of sulfonyl dipoles per side chain, and n-alkyl tail length on the liquid crystalline self-assembly behavior were investigated by comparing iPOPs with their atactic counterparts. First, when the sulfonyl dipole was placed far away from the chiral center in iPOP-SC5SO2Cn compared with our previously reported isotactic polyethers with n-alkylsulfonyl side chains (iPOP-SO2Cn), the dipole–dipole interactions among the side chains decreased, which led to more liquid crystalline phases. Smectic E (SmE) and A (SmA) phases were observed after crystal melting; however, the main-chain chiral center was found to have an insignificant effect on the liquid crystalline assembly when compared to the atactic samples. Second, the longer Cn tails increased the transition temperatures as a result of stronger van der Waals interactions. Third, after the thioether linkage in the side chain was oxidized into the sulfonyl group, the chiral center–dipole and dipole–dipole interactions in the resultant polymers (i.e., iPOP-SO2C5SO2Cn) enhanced. As a result, the liquid crystalline phase transitions (i.e., crystal → SmE → SmA → I) were pushed to higher temperatures. The knowledge gained in this study will help us further design and achieve the ferroelectric smectic C* phase in mesogen-free comb-like sulfonylated liquid crystalline polymers.},
doi = {10.1039/D0PY00199F},
journal = {Polymer Chemistry},
number = 17,
volume = 11,
place = {United States},
year = {2020},
month = {3}
}
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