Non-symmetric dimeric liquid crystals: The preparation and properties of the alpha-(4-cyanobiphenyl-4 '-yloxy)-omega-(4-n-alkylanilinebenzylidene-4 '-oxy) alkanes

G. S. Attard, R. W. Date, Corrie Thomas Imrie, G. R. Luckhurst, S. J. Roskilly, J. M. Seddon, L. Taylor

Research output: Contribution to journalArticle

246 Citations (Scopus)

Abstract

Six series of a family of non-symmetric dimers, the alpha-(4-cyanobiphenyl-4'-yloxy)-omega-(4-n-alkylanilinebenzylidene-4'-oxy) alkanes, have been prepared. In three of the series, the number of methylene groups in the flexible alkyl spacer has been varied from 3 to 12 while the terminal alkyl chain is held constant at either 2, 6 or 10. In the remaining series, the effect of increasing the terminal chain length has been studied by holding the spacer length constant at 3, 4 or 5 methylene units while varying the length of the terminal chain from 0 to 10 carbon atoms. The phase behaviour and transitional properties of these series have been investigated using optical microscopy and differential scanning calorimetry, while the structures of the mesophases have been studied using X-ray diffraction on both powder and aligned samples. This study has revealed novel phase behaviour involving intercalated smectic phases stabilized by the mixed mesogenic group interaction. We have identified the first examples of intercalated smectic C, smectic I, crystal B and crystal J phases and have assigned the layer stacking sequences in the crystal B phases. An extension to the current nomenclature used to describe smectic phases is proposed in order to include these new structural modifications such that, for example, SAc, refers to the intercalated smectic A phase. The specific interaction between the two unlike groups has a much smaller influence on the nematic-isotropic transition temperatures than it has on the structures of the smectic phases. Quantitative estimates of the nematic-isotropic transition temperatures based on the Marcelja-Luckhurst theory provide further evidence for a specific interaction between the unlike mesogenic groups. Finally, the thermal behaviour of binary mixtures of the analogous symmetric dimers is also found to be governed by the mixed core interaction and intercalated smectic phases are observed in these mixtures.

Original languageEnglish
Pages (from-to)529-581
JournalLiquid Crystals
Volume16
Issue number4
DOIs
Publication statusPublished - 1994

Keywords

  • nematogenic molecules
  • orientational order
  • flexible core
  • mesophase
  • model
  • polyesters
  • unit

Cite this

Non-symmetric dimeric liquid crystals : The preparation and properties of the alpha-(4-cyanobiphenyl-4 '-yloxy)-omega-(4-n-alkylanilinebenzylidene-4 '-oxy) alkanes. / Attard, G. S.; Date, R. W.; Imrie, Corrie Thomas; Luckhurst, G. R.; Roskilly, S. J.; Seddon, J. M.; Taylor, L.

In: Liquid Crystals, Vol. 16, No. 4, 1994, p. 529-581.

Research output: Contribution to journalArticle

Attard, G. S. ; Date, R. W. ; Imrie, Corrie Thomas ; Luckhurst, G. R. ; Roskilly, S. J. ; Seddon, J. M. ; Taylor, L. / Non-symmetric dimeric liquid crystals : The preparation and properties of the alpha-(4-cyanobiphenyl-4 '-yloxy)-omega-(4-n-alkylanilinebenzylidene-4 '-oxy) alkanes. In: Liquid Crystals. 1994 ; Vol. 16, No. 4. pp. 529-581.
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abstract = "Six series of a family of non-symmetric dimers, the alpha-(4-cyanobiphenyl-4'-yloxy)-omega-(4-n-alkylanilinebenzylidene-4'-oxy) alkanes, have been prepared. In three of the series, the number of methylene groups in the flexible alkyl spacer has been varied from 3 to 12 while the terminal alkyl chain is held constant at either 2, 6 or 10. In the remaining series, the effect of increasing the terminal chain length has been studied by holding the spacer length constant at 3, 4 or 5 methylene units while varying the length of the terminal chain from 0 to 10 carbon atoms. The phase behaviour and transitional properties of these series have been investigated using optical microscopy and differential scanning calorimetry, while the structures of the mesophases have been studied using X-ray diffraction on both powder and aligned samples. This study has revealed novel phase behaviour involving intercalated smectic phases stabilized by the mixed mesogenic group interaction. We have identified the first examples of intercalated smectic C, smectic I, crystal B and crystal J phases and have assigned the layer stacking sequences in the crystal B phases. An extension to the current nomenclature used to describe smectic phases is proposed in order to include these new structural modifications such that, for example, SAc, refers to the intercalated smectic A phase. The specific interaction between the two unlike groups has a much smaller influence on the nematic-isotropic transition temperatures than it has on the structures of the smectic phases. Quantitative estimates of the nematic-isotropic transition temperatures based on the Marcelja-Luckhurst theory provide further evidence for a specific interaction between the unlike mesogenic groups. Finally, the thermal behaviour of binary mixtures of the analogous symmetric dimers is also found to be governed by the mixed core interaction and intercalated smectic phases are observed in these mixtures.",
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author = "Attard, {G. S.} and Date, {R. W.} and Imrie, {Corrie Thomas} and Luckhurst, {G. R.} and Roskilly, {S. J.} and Seddon, {J. M.} and L. Taylor",
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T2 - The preparation and properties of the alpha-(4-cyanobiphenyl-4 '-yloxy)-omega-(4-n-alkylanilinebenzylidene-4 '-oxy) alkanes

AU - Attard, G. S.

AU - Date, R. W.

AU - Imrie, Corrie Thomas

AU - Luckhurst, G. R.

AU - Roskilly, S. J.

AU - Seddon, J. M.

AU - Taylor, L.

PY - 1994

Y1 - 1994

N2 - Six series of a family of non-symmetric dimers, the alpha-(4-cyanobiphenyl-4'-yloxy)-omega-(4-n-alkylanilinebenzylidene-4'-oxy) alkanes, have been prepared. In three of the series, the number of methylene groups in the flexible alkyl spacer has been varied from 3 to 12 while the terminal alkyl chain is held constant at either 2, 6 or 10. In the remaining series, the effect of increasing the terminal chain length has been studied by holding the spacer length constant at 3, 4 or 5 methylene units while varying the length of the terminal chain from 0 to 10 carbon atoms. The phase behaviour and transitional properties of these series have been investigated using optical microscopy and differential scanning calorimetry, while the structures of the mesophases have been studied using X-ray diffraction on both powder and aligned samples. This study has revealed novel phase behaviour involving intercalated smectic phases stabilized by the mixed mesogenic group interaction. We have identified the first examples of intercalated smectic C, smectic I, crystal B and crystal J phases and have assigned the layer stacking sequences in the crystal B phases. An extension to the current nomenclature used to describe smectic phases is proposed in order to include these new structural modifications such that, for example, SAc, refers to the intercalated smectic A phase. The specific interaction between the two unlike groups has a much smaller influence on the nematic-isotropic transition temperatures than it has on the structures of the smectic phases. Quantitative estimates of the nematic-isotropic transition temperatures based on the Marcelja-Luckhurst theory provide further evidence for a specific interaction between the unlike mesogenic groups. Finally, the thermal behaviour of binary mixtures of the analogous symmetric dimers is also found to be governed by the mixed core interaction and intercalated smectic phases are observed in these mixtures.

AB - Six series of a family of non-symmetric dimers, the alpha-(4-cyanobiphenyl-4'-yloxy)-omega-(4-n-alkylanilinebenzylidene-4'-oxy) alkanes, have been prepared. In three of the series, the number of methylene groups in the flexible alkyl spacer has been varied from 3 to 12 while the terminal alkyl chain is held constant at either 2, 6 or 10. In the remaining series, the effect of increasing the terminal chain length has been studied by holding the spacer length constant at 3, 4 or 5 methylene units while varying the length of the terminal chain from 0 to 10 carbon atoms. The phase behaviour and transitional properties of these series have been investigated using optical microscopy and differential scanning calorimetry, while the structures of the mesophases have been studied using X-ray diffraction on both powder and aligned samples. This study has revealed novel phase behaviour involving intercalated smectic phases stabilized by the mixed mesogenic group interaction. We have identified the first examples of intercalated smectic C, smectic I, crystal B and crystal J phases and have assigned the layer stacking sequences in the crystal B phases. An extension to the current nomenclature used to describe smectic phases is proposed in order to include these new structural modifications such that, for example, SAc, refers to the intercalated smectic A phase. The specific interaction between the two unlike groups has a much smaller influence on the nematic-isotropic transition temperatures than it has on the structures of the smectic phases. Quantitative estimates of the nematic-isotropic transition temperatures based on the Marcelja-Luckhurst theory provide further evidence for a specific interaction between the unlike mesogenic groups. Finally, the thermal behaviour of binary mixtures of the analogous symmetric dimers is also found to be governed by the mixed core interaction and intercalated smectic phases are observed in these mixtures.

KW - nematogenic molecules

KW - orientational order

KW - flexible core

KW - mesophase

KW - model

KW - polyesters

KW - unit

U2 - 10.1080/02678299408036531

DO - 10.1080/02678299408036531

M3 - Article

VL - 16

SP - 529

EP - 581

JO - Liquid Crystals

JF - Liquid Crystals

SN - 0267-8292

IS - 4

ER -