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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. Department of Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive Madison WI 53706-1607 USA
  2. Department of Chemistry and Biochemistry, Kent State University, 1175 Risman Drive Kent OH 44242 USA
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-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
DOE Contract Number:  
AC02-05CH11231; AC02-06CH11357
Resource Type:
Journal Article
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:
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.
@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},
issn = {1616-301X},
number = 13,
volume = 28,
place = {United States},
year = {2018},
month = {1}
}

Works referenced in this record:

Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992


Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a