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Title: Computational Chemistry-Guided Design of Selective Chemoresponsive Liquid Crystals Using Pyridine and Pyrimidine Functional Groups

Abstract

Computational chemistry-guided designs of chemoresponsive liquid crystals (LCs) with pyridine or pyrimidine groups that bind to metal-cation-functionalized surfaces to provide improved selective responses to targeted vapor species (dimethylmethylphosphonate (DMMP)) over nontargeted species (water) are reported. The LC designs against experiments are tested by synthesizing 4-(4-pentyl-phenyl)-pyridine and 5-(4-pentyl-phenyl)-pyrimidine and quantifying LC responses to DMMP and water. Consistent with the computations, pyridine-containing LCs bind to metal-cation-functionalized surfaces too strongly to permit a response to either DMMP or water whereas pyrimidine-containing LCs undergo a surface-driven orientational transition in response to DMMP without interference from water. The computation predictions are not strongly dependent on assumptions regarding the degree of coordination of the metal ions but are limited in their ability to predict LC responses when using cations with mostly empty d orbitals. Overall, this work identifies a promising new class of chemoresponsive LCs based on pyrimidine that exhibits enhanced tolerance to water, a result that is important because water is a ubiquitous and particularly challenging chemical interferent in chemical sensing strategies based on LCs. The work also provides further evidence of the transformative utility of computational chemistry methods to design LC materials that exhibit selective orientational responses in specific chemical environments.

Authors:
 [1]; ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States)
  2. Kent State Univ., Kent, OH (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1543457
Alternate Identifier(s):
OSTI ID: 1417497
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 13; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Science & Technology - Other Topics; Materials Science; Physics

Citation Formats

Yu, Huaizhe, Szilvási, Tibor, Rai, Prabin, Twieg, Robert J., Mavrikakis, Manos, and Abbott, Nicholas L. Computational Chemistry-Guided Design of Selective Chemoresponsive Liquid Crystals Using Pyridine and Pyrimidine Functional Groups. United States: N. p., 2018. Web. doi:10.1002/adfm.201703581.
Yu, Huaizhe, Szilvási, Tibor, Rai, Prabin, Twieg, Robert J., Mavrikakis, Manos, & Abbott, Nicholas L. Computational Chemistry-Guided Design of Selective Chemoresponsive Liquid Crystals Using Pyridine and Pyrimidine Functional Groups. United States. doi:10.1002/adfm.201703581.
Yu, Huaizhe, Szilvási, Tibor, Rai, Prabin, Twieg, Robert J., Mavrikakis, Manos, and Abbott, Nicholas L. Fri . "Computational Chemistry-Guided Design of Selective Chemoresponsive Liquid Crystals Using Pyridine and Pyrimidine Functional Groups". United States. doi:10.1002/adfm.201703581. https://www.osti.gov/servlets/purl/1543457.
@article{osti_1543457,
title = {Computational Chemistry-Guided Design of Selective Chemoresponsive Liquid Crystals Using Pyridine and Pyrimidine Functional Groups},
author = {Yu, Huaizhe and Szilvási, Tibor and Rai, Prabin and Twieg, Robert J. and Mavrikakis, Manos and Abbott, Nicholas L.},
abstractNote = {Computational chemistry-guided designs of chemoresponsive liquid crystals (LCs) with pyridine or pyrimidine groups that bind to metal-cation-functionalized surfaces to provide improved selective responses to targeted vapor species (dimethylmethylphosphonate (DMMP)) over nontargeted species (water) are reported. The LC designs against experiments are tested by synthesizing 4-(4-pentyl-phenyl)-pyridine and 5-(4-pentyl-phenyl)-pyrimidine and quantifying LC responses to DMMP and water. Consistent with the computations, pyridine-containing LCs bind to metal-cation-functionalized surfaces too strongly to permit a response to either DMMP or water whereas pyrimidine-containing LCs undergo a surface-driven orientational transition in response to DMMP without interference from water. The computation predictions are not strongly dependent on assumptions regarding the degree of coordination of the metal ions but are limited in their ability to predict LC responses when using cations with mostly empty d orbitals. Overall, this work identifies a promising new class of chemoresponsive LCs based on pyrimidine that exhibits enhanced tolerance to water, a result that is important because water is a ubiquitous and particularly challenging chemical interferent in chemical sensing strategies based on LCs. The work also provides further evidence of the transformative utility of computational chemistry methods to design LC materials that exhibit selective orientational responses in specific chemical environments.},
doi = {10.1002/adfm.201703581},
journal = {Advanced Functional Materials},
number = 13,
volume = 28,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
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Cited by: 3 works
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Figures / Tables:

Figure 1 Figure 1: (a) Molecular structure of 4’-n-pentyl-4-biphenylcarbonitrile (5CB), 4-(4-pentylphenyl)- pyridine (PD), and 5-(4-pentylphenyl)-pyrimidine (PM). (b) Synthesis ofPD and PM.

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    Works referencing / citing this record:

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