Cyanobiphenyl-based liquid crystal dimers and the twist-bend nematic phase

Daniel A Paterson, Jordan P Abberley, William T A Harrison, John Storey, Corrie T Imrie

Research output: Contribution to journalArticle

62 Citations (Scopus)

Abstract

The synthesis and characterisation of several members of the 1,ω-bis(4-cyanobiphenyl-4′-yl) alkane (CBnCB) and the 1-(4-cyanobiphenyl-4′-yloxy)-ω-(4-cyanobiphenyl-4′-yl) alkane (CBnOCB) homologous series are reported. The new odd members described CB5CB, CB13CB, CB4OCB, CB8OCB and CB10OCB all exhibit twist-bend nematic and nematic phases. The members of these series already reported in literature, CB7CB, CB9CB, CB11CB and CB6OCB, were also prepared in order to allow for a direct comparison of their transitional properties. The properties of these dimers are also compared to those of the corresponding members of the 1,ω-bis(4-cyanobiphenyl-4,-yloxy) alkanes (CBOnOCB). For any given total spacer length, for odd members of these series, the nematic–isotropic transition temperatures and associated entropy changes are greatest for the CBOnOCB dimer and lowest for the CBnCB dimer. These trends are understood in terms of molecular shape. For short spacer lengths, the twist-bend nematic–nematic transition temperature (TNTB N ) is higher for the CBnOCB series than for the CBnCB series but this is reversed as the spacer length increases. Of the CBOnOCB dimers, a virtual value of TNTB N was estimated for CBO3OCB and TNTB N was measured for CBO5OCB. These values are considerably lower than those observed for the corresponding members of the CBnCB or CBnOCB series. The dependence of TNTB N on molecular structure is discussed not only in terms of the molecular curvature but also in the ability of the molecules to pack efficiently. As the temperature range of the preceding nematic phase increases, so the twist-bend nematic–nematic transition entropy change decreases and the transition approaches second order for the longer spacers. For comparative purposes, the transitional behaviour of the even-membered dimers CB6CB, CB5OCB and CBO4OCB is reported and differences accounted for in terms of molecular shape.

Original languageEnglish
Pages (from-to)127-146
Number of pages20
JournalLiquid Crystals
Volume44
Issue number1
Early online date23 Jan 2017
DOIs
Publication statusPublished - 2017

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Liquid Crystals
Dimers
Liquid crystals
spacers
liquid crystals
dimers
Alkanes
Paraffins
alkanes
Superconducting transition temperature
Entropy
transition temperature
entropy
Molecular structure
molecular structure
curvature
trends
Molecules
synthesis
molecules

Keywords

  • cyanobiphenyl
  • liquid crystal dimers
  • molecular modelling
  • twist-bend nematic phase

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Cyanobiphenyl-based liquid crystal dimers and the twist-bend nematic phase. / Paterson, Daniel A; Abberley, Jordan P; Harrison, William T A; Storey, John; Imrie, Corrie T.

In: Liquid Crystals, Vol. 44, No. 1, 2017, p. 127-146.

Research output: Contribution to journalArticle

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T1 - Cyanobiphenyl-based liquid crystal dimers and the twist-bend nematic phase

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AU - Harrison, William T A

AU - Storey, John

AU - Imrie, Corrie T

PY - 2017

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N2 - The synthesis and characterisation of several members of the 1,ω-bis(4-cyanobiphenyl-4′-yl) alkane (CBnCB) and the 1-(4-cyanobiphenyl-4′-yloxy)-ω-(4-cyanobiphenyl-4′-yl) alkane (CBnOCB) homologous series are reported. The new odd members described CB5CB, CB13CB, CB4OCB, CB8OCB and CB10OCB all exhibit twist-bend nematic and nematic phases. The members of these series already reported in literature, CB7CB, CB9CB, CB11CB and CB6OCB, were also prepared in order to allow for a direct comparison of their transitional properties. The properties of these dimers are also compared to those of the corresponding members of the 1,ω-bis(4-cyanobiphenyl-4,-yloxy) alkanes (CBOnOCB). For any given total spacer length, for odd members of these series, the nematic–isotropic transition temperatures and associated entropy changes are greatest for the CBOnOCB dimer and lowest for the CBnCB dimer. These trends are understood in terms of molecular shape. For short spacer lengths, the twist-bend nematic–nematic transition temperature (TNTB N ) is higher for the CBnOCB series than for the CBnCB series but this is reversed as the spacer length increases. Of the CBOnOCB dimers, a virtual value of TNTB N was estimated for CBO3OCB and TNTB N was measured for CBO5OCB. These values are considerably lower than those observed for the corresponding members of the CBnCB or CBnOCB series. The dependence of TNTB N on molecular structure is discussed not only in terms of the molecular curvature but also in the ability of the molecules to pack efficiently. As the temperature range of the preceding nematic phase increases, so the twist-bend nematic–nematic transition entropy change decreases and the transition approaches second order for the longer spacers. For comparative purposes, the transitional behaviour of the even-membered dimers CB6CB, CB5OCB and CBO4OCB is reported and differences accounted for in terms of molecular shape.

AB - The synthesis and characterisation of several members of the 1,ω-bis(4-cyanobiphenyl-4′-yl) alkane (CBnCB) and the 1-(4-cyanobiphenyl-4′-yloxy)-ω-(4-cyanobiphenyl-4′-yl) alkane (CBnOCB) homologous series are reported. The new odd members described CB5CB, CB13CB, CB4OCB, CB8OCB and CB10OCB all exhibit twist-bend nematic and nematic phases. The members of these series already reported in literature, CB7CB, CB9CB, CB11CB and CB6OCB, were also prepared in order to allow for a direct comparison of their transitional properties. The properties of these dimers are also compared to those of the corresponding members of the 1,ω-bis(4-cyanobiphenyl-4,-yloxy) alkanes (CBOnOCB). For any given total spacer length, for odd members of these series, the nematic–isotropic transition temperatures and associated entropy changes are greatest for the CBOnOCB dimer and lowest for the CBnCB dimer. These trends are understood in terms of molecular shape. For short spacer lengths, the twist-bend nematic–nematic transition temperature (TNTB N ) is higher for the CBnOCB series than for the CBnCB series but this is reversed as the spacer length increases. Of the CBOnOCB dimers, a virtual value of TNTB N was estimated for CBO3OCB and TNTB N was measured for CBO5OCB. These values are considerably lower than those observed for the corresponding members of the CBnCB or CBnOCB series. The dependence of TNTB N on molecular structure is discussed not only in terms of the molecular curvature but also in the ability of the molecules to pack efficiently. As the temperature range of the preceding nematic phase increases, so the twist-bend nematic–nematic transition entropy change decreases and the transition approaches second order for the longer spacers. For comparative purposes, the transitional behaviour of the even-membered dimers CB6CB, CB5OCB and CBO4OCB is reported and differences accounted for in terms of molecular shape.

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