Title: Design of Chemoresponsive Liquid Crystals through Integration of Computational Chemistry and Experimental Studies

Abstract

We report the use of computational chemistry methods to design a chemically responsive liquid crystal (LC). Specifically, we used electronic structure calculations to model the binding of nitrile-containing mesogens (4'-n-pentyl-4-biphenylcarbonitrile) to metal perchlorate salts (with explicit description of the perchlorate anion), which we call the coordinately saturated anion model (CSAM). The model results were validated against experimental data. We then used the CSAM to predict that selective fluorination can reduce the strength of binding of nitrile-containing nematic LCs to metal-salt-decorated surfaces and thus generate a faster reordering of the LC in response to competitive binding of dimethylmethylphosphonate (DMMP). We tested this prediction via synthesis of fluorinated compounds 3-fluoro-4'-pentyl[1,1'-biphenyl]-4-carbonitrile and 4-fluoro-4'-pentyl-1,1'-biphenyl, and subsequent experimental measurements of the orientational response of LCs containing these compounds to DMMP. In conclusion, these experimental measurements confirmed the theoretical predictions, thus providing the first demonstration of a chemoresponsive LC system designed from computational chemistry.

Authors:

Szilvási, Tibor ^[1]; Roling, Luke T.  ^[1];

• Search DOE PAGES for author "Roling, Luke T."
• Search DOE PAGES for ORCID "0000-0001-9742-2573"

Yu, Huaizhe ^[1]; Rai, Prabin ^[2]; Choi, Sangwook ^[1]; Twieg, Robert J. ^[2]; Mavrikakis, Manos  ^[1];

• Search DOE PAGES for author "Mavrikakis, Manos"
• Search DOE PAGES for ORCID "0000-0002-5293-5356"

Abbott, Nicholas L.  ^[1]

• Search DOE PAGES for author "Abbott, Nicholas L."
• Search DOE PAGES for ORCID "0000-0002-9653-0326"

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+ Show Author Affiliations

1. Univ. of Wisconsin, Madison, WI (United States)
2. Kent State Univ., Kent, OH (United States)

Publication Date:

Fri Apr 07 00:00:00 EDT 2017

Research Org.:

Univ. of Wisconsin, Madison, WI (United States); Kent State Univ., Kent, OH (United States)

Sponsoring Org.:

National Science Foundation (NSF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

OSTI Identifier:

1418546

Grant/Contract Number:  

AC02-05CH11231; AC02-06CH11357; DMR-1435195

Resource Type:

Accepted Manuscript

Journal Name:

Chemistry of Materials

Additional Journal Information:

Journal Volume: 29; Journal Issue: 8; Journal ID: ISSN 0897-4756

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Mixtures; Salts; Binding energy; Cations; Chromatography