Molecular Flexibility and Bend in Semi‐Rigid Liquid Crystals: Implications for the Heliconical Nematic Ground State

Richard Mandle; John William Goodby

doi:10.1002/chem.201903677

Molecular Flexibility and Bend in Semi‐Rigid Liquid Crystals: Implications for the Heliconical Nematic Ground State

Richard Mandle, John William Goodby

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The NTB phase phases possess a local helical structure with a pitch length of a few nanometers and is typically exhibited by materials consisting of two rigid mesogenic units linked by a flexibile oligomethylene spacer of odd parity, giving a bent shape. We report the synthesis and characterisation of two novel dimeric liquid crystals, and perform a computational study on ten cyanobiphenyl dimers with varying linking groups, generating a large library of conformers for each compound; this allows us to present molecular bend angles as probability weighted averages of many conformers, rather than use a single conformer. We validate conformer libraries by comparison of interproton distances with those obtained from solution based 1D 1H NOESY NMR, finding good agreement between experiment and computational work. Conversely, we find that using any single conformer fails to reproduce experimental interproton distances. We find the use of a single conformer significantly overestimates the molecular bend angle while also ignoring flexibility; we show that the average bend angle and flexibility are both linked to the relative stability of the NTB phase.

Original language	English
Journal	Chemistry : A European Journal
Early online date	4 Sept 2019
DOIs	https://doi.org/10.1002/chem.201903677
Publication status	E-pub ahead of print - 4 Sept 2019

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10.1002/chem.201903677Licence: CC BY

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© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
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Cite this

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title = "Molecular Flexibility and Bend in Semi‐Rigid Liquid Crystals: Implications for the Heliconical Nematic Ground State",

abstract = "The NTB phase phases possess a local helical structure with a pitch length of a few nanometers and is typically exhibited by materials consisting of two rigid mesogenic units linked by a flexibile oligomethylene spacer of odd parity, giving a bent shape. We report the synthesis and characterisation of two novel dimeric liquid crystals, and perform a computational study on ten cyanobiphenyl dimers with varying linking groups, generating a large library of conformers for each compound; this allows us to present molecular bend angles as probability weighted averages of many conformers, rather than use a single conformer. We validate conformer libraries by comparison of interproton distances with those obtained from solution based 1D 1H NOESY NMR, finding good agreement between experiment and computational work. Conversely, we find that using any single conformer fails to reproduce experimental interproton distances. We find the use of a single conformer significantly overestimates the molecular bend angle while also ignoring flexibility; we show that the average bend angle and flexibility are both linked to the relative stability of the NTB phase.",

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N2 - The NTB phase phases possess a local helical structure with a pitch length of a few nanometers and is typically exhibited by materials consisting of two rigid mesogenic units linked by a flexibile oligomethylene spacer of odd parity, giving a bent shape. We report the synthesis and characterisation of two novel dimeric liquid crystals, and perform a computational study on ten cyanobiphenyl dimers with varying linking groups, generating a large library of conformers for each compound; this allows us to present molecular bend angles as probability weighted averages of many conformers, rather than use a single conformer. We validate conformer libraries by comparison of interproton distances with those obtained from solution based 1D 1H NOESY NMR, finding good agreement between experiment and computational work. Conversely, we find that using any single conformer fails to reproduce experimental interproton distances. We find the use of a single conformer significantly overestimates the molecular bend angle while also ignoring flexibility; we show that the average bend angle and flexibility are both linked to the relative stability of the NTB phase.

AB - The NTB phase phases possess a local helical structure with a pitch length of a few nanometers and is typically exhibited by materials consisting of two rigid mesogenic units linked by a flexibile oligomethylene spacer of odd parity, giving a bent shape. We report the synthesis and characterisation of two novel dimeric liquid crystals, and perform a computational study on ten cyanobiphenyl dimers with varying linking groups, generating a large library of conformers for each compound; this allows us to present molecular bend angles as probability weighted averages of many conformers, rather than use a single conformer. We validate conformer libraries by comparison of interproton distances with those obtained from solution based 1D 1H NOESY NMR, finding good agreement between experiment and computational work. Conversely, we find that using any single conformer fails to reproduce experimental interproton distances. We find the use of a single conformer significantly overestimates the molecular bend angle while also ignoring flexibility; we show that the average bend angle and flexibility are both linked to the relative stability of the NTB phase.

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