Hydrogen bonding and liquid crystallinity of low molar mass and polymeric mesogens containing benzoic acids

a variable temperature Fourier transform infrared spectroscopic study

A. Martinez-Felipe, A. G. Cook, M. J. Wallage, C. T. Imrie*

*Corresponding author for this work

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

The phase behaviour and mesomorphism of poly(4-(6-propenoyloxyhexyloxy)benzoic acid) (PPOHBA) and 4-pentyloxybenzoic acid (POBA) is studied using variable-temperature Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction. PPHOBA exhibits a smectic C phase and POBA, a nematic phase. The temperature dependence of the Fermi resonance bands associated with the hydroxyl groups and of the carbonyl stretching region in the FTIR spectra indicates that there is a dynamic equilibrium between monomers and open and closed dimers formed by hydrogen bonding between benzoic acid moieties. The nematic phase observed for POBA is linked to the anisotropic cyclic dimer, while an abrupt increase in the concentration of monomer drives isotropisation. In PPOHBA, hydrogen-bonded supramesogens promote smectic behaviour, while hydrogen-bonded crosslinks stabilise the lamellae. The increased viscosity arising from this dynamic crosslinking is offset by the flexibility of the acrylate backbone and alkyl spacers.

Original languageEnglish
Pages (from-to)1191-1210
Number of pages20
JournalPhase Transitions
Volume87
Issue number12
Early online date21 May 2014
DOIs
Publication statusPublished - 2 Dec 2014

Keywords

  • benzoic acid
  • hydrogen bonding
  • supramolecular liquid crystals
  • side chain liquid crystal polymer
  • temperature-dependent Fourier transform infrared spectroscopy

Cite this

@article{a8135a3daa0f44f7a55ee043a7c95255,
title = "Hydrogen bonding and liquid crystallinity of low molar mass and polymeric mesogens containing benzoic acids: a variable temperature Fourier transform infrared spectroscopic study",
abstract = "The phase behaviour and mesomorphism of poly(4-(6-propenoyloxyhexyloxy)benzoic acid) (PPOHBA) and 4-pentyloxybenzoic acid (POBA) is studied using variable-temperature Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction. PPHOBA exhibits a smectic C phase and POBA, a nematic phase. The temperature dependence of the Fermi resonance bands associated with the hydroxyl groups and of the carbonyl stretching region in the FTIR spectra indicates that there is a dynamic equilibrium between monomers and open and closed dimers formed by hydrogen bonding between benzoic acid moieties. The nematic phase observed for POBA is linked to the anisotropic cyclic dimer, while an abrupt increase in the concentration of monomer drives isotropisation. In PPOHBA, hydrogen-bonded supramesogens promote smectic behaviour, while hydrogen-bonded crosslinks stabilise the lamellae. The increased viscosity arising from this dynamic crosslinking is offset by the flexibility of the acrylate backbone and alkyl spacers.",
keywords = "benzoic acid, hydrogen bonding, supramolecular liquid crystals, side chain liquid crystal polymer, temperature-dependent Fourier transform infrared spectroscopy",
author = "A. Martinez-Felipe and Cook, {A. G.} and Wallage, {M. J.} and Imrie, {C. T.}",
note = "The work is supported by the Spanish Ministry of Science and Innovation through the Research Project, ENE2011-28735-C02-01, the Generalitat Valenciana through the schemes GRISOLIAP/ 2010/057 and APOSTD/2013/054, and UPV through the Research Project PAID-06-11.",
year = "2014",
month = "12",
day = "2",
doi = "10.1080/01411594.2014.900556",
language = "English",
volume = "87",
pages = "1191--1210",
journal = "Phase Transitions",
issn = "0141-1594",
publisher = "TAYLOR & FRANCIS LTD",
number = "12",

}

TY - JOUR

T1 - Hydrogen bonding and liquid crystallinity of low molar mass and polymeric mesogens containing benzoic acids

T2 - a variable temperature Fourier transform infrared spectroscopic study

AU - Martinez-Felipe, A.

AU - Cook, A. G.

AU - Wallage, M. J.

AU - Imrie, C. T.

N1 - The work is supported by the Spanish Ministry of Science and Innovation through the Research Project, ENE2011-28735-C02-01, the Generalitat Valenciana through the schemes GRISOLIAP/ 2010/057 and APOSTD/2013/054, and UPV through the Research Project PAID-06-11.

PY - 2014/12/2

Y1 - 2014/12/2

N2 - The phase behaviour and mesomorphism of poly(4-(6-propenoyloxyhexyloxy)benzoic acid) (PPOHBA) and 4-pentyloxybenzoic acid (POBA) is studied using variable-temperature Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction. PPHOBA exhibits a smectic C phase and POBA, a nematic phase. The temperature dependence of the Fermi resonance bands associated with the hydroxyl groups and of the carbonyl stretching region in the FTIR spectra indicates that there is a dynamic equilibrium between monomers and open and closed dimers formed by hydrogen bonding between benzoic acid moieties. The nematic phase observed for POBA is linked to the anisotropic cyclic dimer, while an abrupt increase in the concentration of monomer drives isotropisation. In PPOHBA, hydrogen-bonded supramesogens promote smectic behaviour, while hydrogen-bonded crosslinks stabilise the lamellae. The increased viscosity arising from this dynamic crosslinking is offset by the flexibility of the acrylate backbone and alkyl spacers.

AB - The phase behaviour and mesomorphism of poly(4-(6-propenoyloxyhexyloxy)benzoic acid) (PPOHBA) and 4-pentyloxybenzoic acid (POBA) is studied using variable-temperature Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction. PPHOBA exhibits a smectic C phase and POBA, a nematic phase. The temperature dependence of the Fermi resonance bands associated with the hydroxyl groups and of the carbonyl stretching region in the FTIR spectra indicates that there is a dynamic equilibrium between monomers and open and closed dimers formed by hydrogen bonding between benzoic acid moieties. The nematic phase observed for POBA is linked to the anisotropic cyclic dimer, while an abrupt increase in the concentration of monomer drives isotropisation. In PPOHBA, hydrogen-bonded supramesogens promote smectic behaviour, while hydrogen-bonded crosslinks stabilise the lamellae. The increased viscosity arising from this dynamic crosslinking is offset by the flexibility of the acrylate backbone and alkyl spacers.

KW - benzoic acid

KW - hydrogen bonding

KW - supramolecular liquid crystals

KW - side chain liquid crystal polymer

KW - temperature-dependent Fourier transform infrared spectroscopy

U2 - 10.1080/01411594.2014.900556

DO - 10.1080/01411594.2014.900556

M3 - Article

VL - 87

SP - 1191

EP - 1210

JO - Phase Transitions

JF - Phase Transitions

SN - 0141-1594

IS - 12

ER -