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

Szilvási, Tibor; Roling, Luke T.; Yu, Huaizhe; Rai, Prabin; Choi, Sangwook; Twieg, Robert J.; Mavrikakis, Manos; Abbott, Nicholas L.

doi:10.1021/acs.chemmater.6b05430

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

Journal Article · Fri Apr 07 00:00:00 EDT 2017 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.6b05430· OSTI ID:1418546

Szilvási, Tibor ^[1]; ^[2]; Yu, Huaizhe ^[2]; Rai, Prabin ^[3]; Choi, Sangwook ^[2]; Twieg, Robert J. ^[3]; ^[2]; ^[2]

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

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.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1418546

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 8 Vol. 29; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Biphenylyl-1,2,4-oxadiazole based liquid crystals – synthesis, mesomorphism, effect of lateral monofluorination Fouad, Farid S.; Ness, Todd; Wang, Kunlun Taylor & Francis https://doi.org/10.6084/m9.figshare.8220881	text	January 2019
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