p-Methoxy Azobenzene Terpolymer as a Promising Energy-Storage Liquid Crystal System

A. Ramadan Ibrahim, M. Faisal Khyasudeen, John Husband, Sakinah Mohd Alauddin, Nurul Fadhilah Kamalul Aripin, Thamil Selvi Velayutham, Alfonso Martinez-Felipe, Osama K. Abou-Zied* (Corresponding Author)

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

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Light-responsive materials capable of undergoing photoinduced molecular transformation are excellent candidates for energy storage. Herein, we report a promising new liquid crystalline terpolymer that is capable of trapping the absorbed photon energy upon exposure to UV light through trans → cis isomerization and molecular aggregation. MeOAzB-T (contains p-methoxyazobenzene, 2-acrylamido-2-methyl-1-propanesulfonic acid, and methyl(methacrylate) monomeric units) shows a trans ← cis normal thermal recovery in solution (THF) after UV exposure, whereas in the glassy state (at 22 °C) and smectic phase (at 75 °C), the recovery process indicates an unusual increase in absorbance of the trans isomer. Surprisingly, when the smectic phase was cooled down to the glassy state while maintaining UV exposure, the increase in absorbance of the trans isomer was maintained at the same level in the dark (monitored for 20 days) until the sample was heated to 75 °C and then cooled to 22 °C in which a full recovery was achieved. Enhancement of H- and J-aggregations of the trans-MeOAzB units was found to be responsible for the absorbance increase. Both forms of aggregation have absorbance signatures and were reproduced by time-dependent density functional theory (TD-DFT). A long lifetime component was detected in the femtosecond transient absorption (TA) spectra in thin films (215 ps in the glass state and 97 ps in the smectic phase) and was assigned to a long-lived intermediate state as a result of aggregation. The stability of the excited state leads to more aggregation as a consequence of the larger dipole moment, compared to the ground state, which is manifested in the TD-DFT calculations as an increase in electron density at the central azo bond. The current results suggest that aggregation after UV irradiation can be maintained for a long time at room temperature and can be relaxed to the original configuration by heating above the glass transition, showing the suitability of MeOAzB-T as a solar thermal fuel.
Original languageEnglish
Pages (from-to)22472–22482
Number of pages11
JournalThe Journal of Physical Chemistry C
Issue number41
Early online date11 Oct 2021
Publication statusPublished - 21 Oct 2021

Bibliographical note

OKAZ, JH, and ARI would like to acknowledge the Sultan Qaboos University for its support through His Majesty’s Trust Fund for Strategic Research (SR/SCI/CHEM/18/01) and Internal Grant (IG/SCI/CHEM/21/03). SMA and NFKA would like to acknowledge Malaysian Ministry of Higher Education for the grant number 600-IRMI/FRGS 5/3 (374/2019). AMF would like to acknowledge the Carnegie Trust for the Universities of Scotland, for the Research Incentive Grant RIG008586, the Royal Society and Specac Ltd., for the Research Grant GS\R1\201397, the Royal Society of Chemistry for the award of a mobility grant (M19-0000), and the Royal Society of Edinburgh and the Scottish Government, for the award of a SAPHIRE project.


  • side-chain liquid crystal polymers
  • azobenzene
  • energy storage
  • absorption spectroscopy
  • density functional theory
  • ultrafast dynamics
  • dielectric response


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