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Light-Controlled Lyotropic Liquid Crystallinity of Polyaspartates Exploited as Photo-Switchable Alignment Medium

  • Max Hirschmann
    Max Hirschmann
    Clemens-Schöpf-Institute, Technical University of Darmstadt (TUDa), Alarich-Weiss-Straße 4, DE 64287 Darmstadt, Germany
  • Olaf Soltwedel
    Olaf Soltwedel
    Institute for Condensed Matter Physics, Technical University of Darmstadt (TUDa), Hochschulstraße 8, DE 64289 Darmstadt, Germany
  • Philipp Ritzert
    Philipp Ritzert
    Institute for Condensed Matter Physics, Technical University of Darmstadt (TUDa), Hochschulstraße 8, DE 64289 Darmstadt, Germany
  • Regine von Klitzing
    Regine von Klitzing
    Institute for Condensed Matter Physics, Technical University of Darmstadt (TUDa), Hochschulstraße 8, DE 64289 Darmstadt, Germany
  • , and 
  • Christina M. Thiele*
    Christina M. Thiele
    Clemens-Schöpf-Institute, Technical University of Darmstadt (TUDa), Alarich-Weiss-Straße 4, DE 64287 Darmstadt, Germany
    *Email: [email protected]
Cite this: J. Am. Chem. Soc. 2023, 145, 6, 3615–3623
Publication Date (Web):February 7, 2023
https://doi.org/10.1021/jacs.2c12760
Copyright © 2023 The Authors. Published by American Chemical Society

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    Abstract

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    Two polyaspartates bearing ortho-fluorinated azobenzenes (pFAB) as photo-responsive groups in the side chain were synthesized: PpFABLA (1) and co-polyaspartate PpFABLA-co-PBLA [11, 75%(n/n) PpFABLA content]. As a consequence of the E/Z-isomerization of the side chain, PpFABLA (1) undergoes a visible-light-induced reversible coil–helix transition in solution: Green light (525 nm) affords the coil, and violet light (400 nm) affords the helix. pFAB significantly increases the thermal stability of the Z-isomer at 20 °C (t1/2 = 66 d for the Z-isomer) and effectively counters the favored back formation of the helix. At 20%(w/w) polymer concentration, the helical polymer forms a lyotropic liquid crystal (LLC) that further orients unidirectionally inside a magnetic field, while the coil polymer results in an isotropic solution. The high viscosity of the polymer solution stabilizes the coexistence of liquid crystalline and isotropic domains, which were obtained with spatial control by partial light irradiation. When used as an alignment medium, PpFABLA (1) enables (i) the measurement of dipolar couplings without the need for a separate isotropic reference and (ii) the differentiation of enantiomers. PpFABLA-co-PBLA (11) preserves the helical structure, by intention, independently of the E/Z-isomerization of the side chain: Both photo-isomers of PpFABLA-co-PBLA (11) form a helix that─at a concentration of 16%(w/w)─form an LLC. Despite the absence of a change in the secondary structure, the E/Z-isomerization of the side chain changes the morphology of the liquid crystal and leads to different sets of dipolar coupling for the same probe molecule.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.2c12760.

    • Details on materials; synthetic and analytical procedures; characterization data; sample preparation; in situ irradiation NMR, POM, AFM, SAXS, UV–vis and CD set-up/data; RDC analysis (PDF)

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    Cited By

    This article is cited by 2 publications.

    1. Ruggero Rossi, Daniele Martella, Camilla Parmeggiani, Max Hirschmann, Tiziana Fuoco. Photoswitches in Order: One-Pot Synthesis of Azobenzene Main-Chain and Segmented Copolymers. ACS Applied Polymer Materials 2024, 6 (2) , 1563-1572. https://doi.org/10.1021/acsapm.3c02849
    2. Si-Yong Qin, Jin-Hao He, You Zhao, Yan-Ling Yang, Ai-Qing Zhang, Xinxiang Lei. Programming Peptide Liquid Crystal Media to Acquire Independent Sets of Residual Dipolar Couplings and Enantiodiscrimination in Multiple Solvent Systems. Analytical Chemistry 2023, 95 (48) , 17759-17765. https://doi.org/10.1021/acs.analchem.3c03777