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Digital photoprogramming of liquid-crystal superstructures featuring intrinsic chiral photoswitches

Nature Photonics volume 16, pages 226–234 (2022)Cite this article

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Abstract

Dynamic patterning of soft materials in a fully reversible and programmable manner with light enables applications in anti-counterfeiting, displays and labelling technology. However, this is a formidable challenge due to the lack of suitable chiral molecular photoswitches. Here, we report the development of a unique intrinsic chiral photoswitch with broad chirality modulation to achieve digitally controllable, selectable and extractable multiple stable reflection states. An anti-counterfeiting technique, embedded with diverse microstructures, featuring colour-tunability, erasability, reversibility, multi-stability and viewing-angle dependency of pre-recorded patterns, is established with these photoresponsive superstructures. This strategy allows dynamic helical transformation from the molecular and supramolecular to the macroscopic level using light-activated intrinsic chirality, demonstrating the practicality of photoprogramming photonics.

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Fig. 1: Intrinsic chirality endowing the photoswitch with unique features for photoprogrammable LC helical superstructures.
Fig. 2: HPLC, CD spectra, fatigue resistance and thermal stability comparisons: intrinsic chirality versus extrinsic chiral groups.
Fig. 3: Dynamic and reversible light control of the helical LC superstructure with multi-stability.
Fig. 4: Photoprogramming and modulation capabilities of photoswitch (M)-1o enable the reconfiguration of optical microstructures with highly efficient diffraction and microcavity features.
Fig. 5: Multiple anti-counterfeiting characteristics with light-induced pattern emergence and hiding, colour-tunability and reversibility, digitalized extraction, viewing-angle-dependent reflectance as well as embedded hidden microstructures.

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All data needed to evaluate the conclusions in the paper are present in the paper and the Supplementary Information.

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Acknowledgements

This work was supported by the NSFC (21788102, 21636002, 61822504, 51873060 and 21702059), the Shanghai Municipal Science and Technology Major Project (2018SHZDZX03 and 21JC1401700), the Innovation Program of the Shanghai Municipal Education Commission, the Scientific Committee of Shanghai (15XD1501400 and 2021-01-07-00-02-E00107), the China Postdoctoral Science Foundation (2019M661399), the Shanghai Sailing Program (20YF1410500) and the ‘Shuguang Program’ of the Shanghai Education Development Foundation and Shanghai Municipal Education Commission (21SG29). B.L.F. thanks the financial support from the European Research Council (ERC; advanced grant no. 694345 to B.L.F.) and the Dutch Ministry of Education, Culture and Science (Gravitation program no. 024.001.035). We thank A. Lubbe and Q. Zhang for their suggestions.

Author information

Author notes

  1. These authors contributed equally: Zhigang Zheng, Honglong Hu, Zhipeng Zhang.

Authors and Affiliations

  1. Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Institute of Fine Chemicals, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, China

    Zhigang Zheng, Honglong Hu, Zhipeng Zhang, Mengqi Li, Da-Hui Qu, He Tian, Wei-Hong Zhu & Ben L. Feringa

  2. School of Physics, East China University of Science and Technology, Shanghai, China

    Zhigang Zheng & Binghui Liu

  3. Centre for Systems Chemistry, Stratingh Institute for Chemistry and Zernike Institute for Advanced Materials, Faculty of Mathematics and Natural Sciences, University of Groningen, Groningen, The Netherlands

    Ben L. Feringa

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Contributions

Z. Zheng, W.-H.Z. and B.L.F. conceived and supervised the research. B.L.F., H.T., W.-H.Z., D.-H.Q., Z. Zheng, H.H. and Z. Zhang prepared the manuscript. H.H., B.L. and M.L. carried out the experiments. Z. Zheng, H.H., Z. Zhang, B.L. and W.-H.Z. conducted the data analysis.

Corresponding authors

Correspondence to Wei-Hong Zhu or Ben L. Feringa.

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Extended data

Extended Data Fig. 1 HPLC, CD spectra, fatigue resistance and thermal stability comparisons: intrinsic chirality vs. extrinsic chiral groups.

a, Chiral HPLC chromatograms of (M)-2o, (CH3CN, monitored at the isobestic point of 340 nm). b, Chiral HPLC chromatograms of (M)-3o (CH3CN : H2O=80 : 20, 0.5 mL min−1, monitored at the isobestic point of 303 nm). c, d, The circular dichroism spectra of (M)-2o and (M)-3o. e, f, Fatigue resistance of (M)-2o and (M)-3o in tetrahydrofuran at 2.0 × 10−5 M. The photoswitches were irradiated with UV (λ = 313 ± 10 nm) light and visible (λ > 480 nm) light and the detected value is the maximum absorption in the visible region.

Source data

Extended Data Fig. 2 Dynamic controlling of reflection wavelength through light switchable intrinsic chirality.

Reflection wavelength of a, 0.62 mol% of (M)-2o, b, 1.44 mol% of (M)-3o, c, 0.77 mol% of (S,S)-4o, in the twisted nematic LC (LCM17, commercially from PhiChem, Shanghai) in a 4.9 μm thick planar cell upon exposure to 365 nm (4.0 mW cm−2) with different times and the recovery was achieved by a 530 nm (1.0 mW cm−2) visible light irradiation corresponding to (d-f).

Source data

Supplementary information

Supplementary Information

Supplementary text, Figs. 1–34, Tables 1–11 and refs. 1–4.

Supplementary Video 1

Reflection colour change of the oily-streak texture.

Supplementary Video 2

‘ECUST’ QR code anti-counterfeiting observed at the Bragg angle.

Supplementary Video 3

‘ECUST’ QR code anti-counterfeiting observed deviated from the Bragg angle.

Supplementary Video 4

Scanning of ‘ECUST’ QR code image.

Supplementary Video 5

‘ECUST’ QR code anti-counterfeiting observed after half a year.

Supplementary Video 6

Anti-counterfeiting of embedding invisible microstructures into the ‘ECUST’ QR code.

Supplementary Video 7

Scanning of ‘ECUST’ QR code in LC cell.

Supplementary Video 8

‘WINE’ QR code anti-counterfeiting on wine.

Supplementary Video 9

Anti-counterfeiting of tree image on Chinese baijiu (Chinese liquor).

Supplementary Data 1

Crystallographic data of 1o.

Supplementary Data 2

Crystallographic data of 1c.

Supplementary Data 3

Raw 1H NMR data of (M)-1o.

Supplementary Data 4

Raw 1H NMR data of (M)-2o.

Source data

Source Data Fig. 2

Unprocessed statistical source data of Fig. 2.

Source Data Fig. 3

Unprocessed statistical source data of Fig. 3.

Source Data Fig. 4

Unprocessed statistical source data of Fig. 4.

Source Data Extended Data Fig. 1

Unprocessed statistical source data of Extended Data Fig. 1.

Source Data Extended Data Fig. 2

Unprocessed statistical source data of Extended Data Fig. 2.

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Zheng, Z., Hu, H., Zhang, Z. et al. Digital photoprogramming of liquid-crystal superstructures featuring intrinsic chiral photoswitches. Nat. Photon. 16, 226–234 (2022). https://doi.org/10.1038/s41566-022-00957-5

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