Long Alkyl Tails Amplify Photoswitchable Glass Transition Temperatures of Azopolymers for Nanoimprint Lithography

Zhu-Lu Xie; Fu-Wei Kong; Jia-Hui Chen; Jie Yan; Bo-Ting Wang; Tian-Ren Zhao; Shuo-Feng Liang; Si Wu

doi:10.1007/s10118-026-3637-2

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Long Alkyl Tails Amplify Photoswitchable Glass Transition Temperatures of Azopolymers for Nanoimprint Lithography

RESEARCH ARTICLE | Updated：2026-07-01

- Long Alkyl Tails Amplify Photoswitchable Glass Transition Temperatures of Azopolymers for Nanoimprint Lithography
- Chinese Journal of Polymer Science Vol. 44, Issue 7, Pages: 2239-2247(2026)
- Affiliations：
  
  Hefei National Research Center for Physical Sciences at the Microscale, Anhui Key Laboratory of Optoelectronic Science and Technology, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China
- Author bio：
  
  liangsf@ustc.edu.cn (S.F.L.)
  siwu@ustc.edu.cn (S.W.)
- Funds：
- DOI：10.1007/s10118-026-3637-2
  CLC：
- Received：03 February 2026，
  
  Accepted：27 February 2026，
  
  Online First：03 June 2026，
  
  Published：05 July 2026
- Accepted：
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Xie, Z. L.; Kong, F. W.; Chen, J. H.; Yan, J.; Wang, B. T.; Zhao, T. R.; Liang, S. F.; Wu, S. Long alkyl tails amplify photoswitchable glass transition temperatures of azopolymers for nanoimprint lithography. Chinese J. Polym. Sci. 2026, 44, 2239–2247

Zhu-Lu Xie, Fu-Wei Kong, Jia-Hui Chen, et al. Long Alkyl Tails Amplify Photoswitchable Glass Transition Temperatures of Azopolymers for Nanoimprint Lithography[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2239-2247.
Xie, Z. L.; Kong, F. W.; Chen, J. H.; Yan, J.; Wang, B. T.; Zhao, T. R.; Liang, S. F.; Wu, S. Long alkyl tails amplify photoswitchable glass transition temperatures of azopolymers for nanoimprint lithography. Chinese J. Polym. Sci. 2026, 44, 2239–2247 DOI： 10.1007/s10118-026-3637-2.

Zhu-Lu Xie, Fu-Wei Kong, Jia-Hui Chen, et al. Long Alkyl Tails Amplify Photoswitchable Glass Transition Temperatures of Azopolymers for Nanoimprint Lithography[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2239-2247. DOI： 10.1007/s10118-026-3637-2.

摘要

Azobenzene-containing polymers exhibit photoswitchable glass-transition temperatures when modified with long alkyl tails. This tail-engineering approach fundamentally overcomes the spacer length limitations and establishes a generalizable design principle for reversible nanoimprint photoresists.

Abstract

Azobenzene-containing polymers (azopolymers) exhibit photoinduced reversible solid-to-liquid transitions

enabling unique light-assisted nanoimprint lithography (NIL).

Cis

azopolymers possess sub-room-temperature glass transition temperatures (

)

exhibiting liquid-like behavior for flow processing

while

trans

azopolymers feature above-room-temperature

values that enable solid-state shape fixation. Although many side-chain azopolymers demonstrate photoswitchable

conventional short-spacer derivatives show negligible switching in

as their

cis

isomers remain solid. This work overcomes this limitation in ethylene-spacer azopolymers through extended alkyl tails. We synthesized tailless (P0)

-butyl-tailed (P4)

and

-decyl-tailed (P10) derivatives

revealing that only P10 exhibits a

cis

near room temperature (22 °C) and an amplified Δ

between its

cis

isomer and

trans

isomer. P10 with photoswitchable

s enables complete nanostructure replication as a nanoimprint lithography photoresist. This work demonstrates that long alkyl tails counteract short-spacer limitations

effectively reducing the

cis

azopolymers and establishing a design principle for nanoimprint photoresists with photoswitchable

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references

Napolitano, S.; Glynos, E.; Tito, N. B. Glass transition of polymers in bulk, confined geometries, and near interfaces. Rep. Prog. Phys. 2017 , 80 , 036602..

Traub, M. C.; Longsine, W.; Truskett, V. N. Advances in nanoimprint lithography. Annu. Rev. Chem. Biomol. Eng. 2016 , 7 , 583−604..

Liang, S.; Yuan, C.; Nie, C.; Liu, Y.; Zhang, D.; Xu, W.-C.; Liu, C.; Xu, G.; Wu, S. Photocontrolled reversible solid-fluid transitions of azopolymer nanocomposites for intelligent nanomaterials. Adv. Mater. 2024 , 36 , e2408159..

Xu, W.-C.; Liu, C.; Liang, S.; Zhang, D.; Liu, Y.; Wu , S. Designing rewritable dual-mode patterns using a stretchable photoresponsive polymer via orthogonal photopatterning. Adv. Mater. 2022 , 34 , 2202150..

Zhou, H.; Xue, C.; Weis, P.; Suzuki, Y.; Huang, S.; Koynov, K.; Auernhammer, G. K.; Berger, R.; Butt, H. J.; Wu, S. Photoswitching of glass transition temperatures of azobenzene-containing polymers induces reversible solid-to-liquid transitions. Nat. Chem. 2017 , 9 , 145−151..

Xu, W. C.; Sun, S.; Wu, S. Photoinduced reversible solid-to-liquid transitions for photoswitchable materials. Angew. Chem. Int. Ed. 2019 , 58 , 9712−9740..

Bandara, H. M. D.; Burdette, S. C. Photoisomerization in different classes of azobenzene. Chem. Soc. Rev. 2012 , 41 , 1809−1825..

Jerca, F. A.; Jerca, V. V.; Hoogenboom, R. Advances and opportunities in the exciting world of azobenzenes. Nat. Rev. Chem. 2021 , 6 , 51−69..

Dang, T.; Zhang, Z.-Y.; Li, T. Visible-light-activated heteroaryl azoswitches: toward a more colorful future. J. Am. Chem. Soc. 2024 , 146 , 19609−19620..

[Liang, S.; Yuan, C.; Wang, M.; Wu, S. Photoresponsive polymer nanocomposites: dynamic materials with photocontrolled functions. CCS Chem . 2025 , 7 , 2950−2969..

Yue, Y.; Norikane, Y.; Nishibori, E. Biomimetic adhesion/detachment using layered polymers with light-induced rapid shape changes. Angew. Chem. Int. Ed. 2025 , 64 , e202503748..

Lin, Z.; Feng, J.; Fang, L.; Zhang, Y.; Ran, Q.; Zhu, Q.; Yu, D. Transforming commercial polymers into tough yet switchable adhesives by trident photoswitch molecule doping: break adhesion-switchability paradox. Adv. Mater. 2024 , 36 , e2406459..

Zhao, R.; Mu, J.; Bai, J.; Zhao, W.; Gong, P.; Chen, L.; Zhang, N.; Shang, X.; Liu, F.; Yan, S. Smart responsive azo-copolymer with photoliquefaction for switchable adhesive application. ACS Appl. Mater. Interfaces 2022 , 14 , 16678−16686..

Shen, D.; Yao, Y.; Zhuang, Q.; Lin, S. Mainchain alternating azopolymers with fast photo-i nduced reversible transition behavior. Macromolecules 2021 , 54 , 10040−10048..

Zhou, J.; Zhou, N.; Xu, W.; Qian, Z.; Dai, Z.; Xu, J.; Chen, J.; Xiong, Y. Photo-tuned solid-liquid transition of azo-grafted poly(thioctic acid) with ultrahigh photothermal conversion efficiency. Angew. Chem. Int. Ed. 2025 , 64 , e202508314..

Hsu, Y. S.; Tsai, T. H.; Chang, C. C.; Lo, T. Y.; Kuo, K. C.; Lin, Y. C.; Lin, J.; Manibalan, K.; Chang, C. W.; Ho, J. H.;Lin, C. T.; Chen, J. T. Photo-healable and stretchable fibers from upcycled tpee and azopolymers by harnessing solid-to-liquid photoisomerization. ACS Appl. Mater. Interfaces 2025 , 17 , 51256−51266..

Chen, M.; Yao, B.; Kappl, M.; Liu, S.; Yuan, J.; Berger, R.; Zhang, F.; Butt, H.-J.; Liu, Y.; Wu, S. Entangled azobenzene-containing polymers with photoinduced reversible solid-to-liquid transitions for healable and reprocessable photoactuators. Adv. Funct. Mater. 2019 , 30 , 201906752..

Liu, Y.; Liang, S.; Yuan, C.; Best, A.; Kappl, M.; Koynov, K.; Butt, H.-J.; Wu, S. Fabrication of anticounterfeiting nanocomposites with multiple security features via integration of a photoresponsive polymer and upconverting nanoparticles. Adv. Funct. Mater. 2021 , 31 , 2103908..

Xu, X.; Li, C.; Chen, W.; Feng, J.; Li, W.-Y.; Wang, G.; Yu, H. Visible light activated dendrimers for solar thermal energy storage and release below 0 °C. J. Mater. Chem. A 2024 , 12 , 23723−23731..

Cai, F.; Song, T.; Yang, B.; Lv, X.; Zhang, L.; Yu, H. Enhancement of solar thermal fuel by microphase separation and nanoconfinement of a block copolymer. Chem. Mater. 2021 , 33 , 9750−9759..

Zhang, Z.-Y.; He, Y.; Wang, Z.; Xu, J.; Xie, M.; Tao, P.; Ji, D.; Moth-Poulsen, K.; Li, T. Photochemical phase transitions enable coharvesting of photon energy and ambient heat for energetic molecular solar thermal batteries that upgrade thermal energy. J. Am. Chem. Soc. 2020 , 142 , 12256−12264..

Han, G. G. D.; Li, H.; Grossman, J. C. Optically-controlled long-term storage and release of thermal energy in phase-change materials. Nat. Commun. 2017 , 8 , 1446..

Chen, C.; Ji, Y.; Li, H.; Song, T.; Yu, H. Unusual photo-tunable mechanical transformation of azobenzene t erminated aliphatic polycarbonate. Nat. Commun. 2025 , 16 , 2620..

Cai, F.; Yang, B.; Lv, X.; Feng, W.; Yu, H. Mechanically mutable polymer enabled by light. Sci. Adv. 2022 , 8 , eabo1626..

Ji, Y.; Song, T.; Yu, H. Assembly-induced dynamic structural color in a host-guest system for time-dependent anticounterfeiting and double-lock encryption. Angew. Chem. Int. Ed. 2024 , 63 , e202401208..

Pan, F.; Feng, Y.; Qian, Y.; Qin, L.; Yu, Y. Dual-mode patterns enabled by photofluidization of an azobenzene-containing linear liquid crystal copolymer. Langmuir 2024 , 40 , 11766−11774..

Yuan, C.; Zhang, D.; Xie, Z.; Xu, W.-C.; Liang, S.; Wu, S. Heterogeneous polymer multilayers enabling photoresponsive nonreciprocal patterns forinformation encryption. Adv. Mater. 2025 , 37 , e2506950..

Ji, B.; Qin, L.; Yu, Y. L. Dynamic structural colors in helical superstructures: from supramolecules to polymers. Chinese J. Polym. Sci. 2025 , 43 , 406−428..

[Lugger, S. J. D.; Ceamanos, L.; Mulder, D. J.; Sánchez-Somolinos, C.; Schenning, A. P. H. J. 4D printing of supramolecular liquid crystal elastomer actuators fueled by light. Adv. Mater. Technol . 2022, 8 , 2201472..

Zhao, X.; Chen, Y.; Peng, B.; Wei, J.; Yu, Y. A facile strategy for the development of recyclable multifunctional liquid crystal polymers via post-polymerization modification and ring-opening metathesis polymerization. Angew. Chem. Int. Ed. 2023 , 62 , e202300699..

Guo, H.; Nasare, R.; Liang, C.; Kuntze, K.; Terentjev, E. M.; Priimagi, A. Halogen-bonded liquid crystal elastomers as initiator-free photochemical actuators. Adv. Mater. 2025 , 37 , e2504551..

Qu, G.; Zhang, X.; Li, S.; Lu, L.; Gao, J.; Yu, B.; Wu, S.; Zhang, Q.; Hu, Z. Liquid crystal random lasers. Phys. Chem. Chem. Phys. 2022 , 25 , 48−63..

[Gao, M. D.; Guan, C. Y.; Wang, J. Y.; Qi, J. Y.; Deng, N. N. Thermally switchable photoactivity in azobenzene-functionalized dna condensates. Adv. Mater . 2025, e18318..

Li, H. T.; Zhang, W. L.; He, Y. N. Non-covalently functionalized carbon nanotube by hyaluronic acid based azo polymer for photothermal elimination of tumor cells. Chinese J. Polym. Sci. 2025 , 43 , 1785−1791..

Sun, Z.; Xu, Z.; Ding, M.; Wang, L.; Zhao, L.; Sui, P.; Li, G.; Jin, H.; Zhou, Y.; Lin, S. Ultrathin polymersomes with controllable light-responsivity via adjusting the electronic effect from para-substituents of azobenzene. Angew. Chem. Int. Ed. 2025 , 64 , e202503104..

Zhao, Q. H.; Qi, J. Y.; Deng, N. N. DNA photofluids show life-like motion. Nat. Mater. 2025 , 24 , 935−944..

Liu, C.; Yang, Z.; Song, X.; Qian, Y.; Huo, H.; He, J.; Zhang, J.; Zhang, Z.; Shi, M.; Pang, J.; Zhang, B.; Tian, W. Light controlled drug-based supramolecular polymer self-assemblies for efficient antibacterial manipulation. Supramol. Mater. 2022 , 1 , 100014..

Ma, W.; Wang, B.; Wang, D.; Liu, Y.; Jiang, M.-C.; Zhang, J.-Y.; Pen g, D.-D.; Li, Z.-C.; Yu, C.-Y.; Wei, H. A self-cascade terpolymer platform for amplified chemo-chemodynamic therapy with synergistic immunogenic cell death enhancement. Supramol. Mater. 2024 , 3 , 100066..

Cheng, X.; Miao, T.; Zhang, G.; Guo, J.; Zhou, Z.; Zhang, W. Switchable Phase Helicity Independent of the Absolute Configuration of the Stereocenter: anomalous induction between sergeants and soldiers in chiral liquid-crystalline polymers. J. Am. Chem. Soc. 2023 , 145 , 16474−16487..

Lee, S.; Kang, H. S.; Park, J. K. Directional photofluidization lithography: micro/nanostructural evolution by photofluidic motions of azobenzene materials. Adv. Mater. 2012 , 24 , 2069−2103..

Kang, H. S.; Jolly, J. C.; Cho, H.; Kalpattu, A.; Zhang, X. A.; Yang, S. Three-Dimensional Photoengraving of Monolithic, Multifaceted Metasurfaces. Adv. Mater. 2020 , 33 , 202005454..

Liang, S. F.; Nie, C.; Yan, J.; Zhang, Q. J.; Wu, S. Photoinduced reversible solid-to-liquid transitions and directional photofluidization of azobenzene-containing polymers. Chinese J. Polym. Sci. 2020 , 39 , 1225−1234..

Weis, P.; Hess, A.; Kircher, G.; Huang, S.; Auernhammer, G. K.; Koynov, K.; Butt, H.-J.; Wu, S. Effects of spacers on photoinduced reversible solid-to-liquid transitions of azobenzene-containing polymers. Chem. - Eur. J. 2019 , 25 , 10946−10953..

Zhang, Z.; Chen, M.; Schneider, I.; Liu, Y.; Liang, S.; Sun, S.; Koynov, K.; Butt, H.-J.; Wu, S. Long alkyl side chains simultaneously improve mechanical robustness and healing ability of a photoswitchable polymer. Macromolecules 2020 , 53 , 8562−8569..

Liang, S.; Li, S.; Yuan, C.; Zhang, D.; Chen, J.; Wu, S. Polyacrylate backbone promotes photoinduced reversible solid-to-liquid transitions of azobenzene-containing polymers. Macromolecules 2023 , 56 , 448−456..

Liu, C.; Steppert, A. K.; Liu, Y.; Weis, P.; Hu, J.; Nie, C.; Xu, W.-C.; Kuehne, A. J. C.; Wu, S. A Photopatternable conjugated polymer with thermal-annealing-promoted interchain stacking for highly stable anti-counterfeiting materials. Adv. Mater. 2023 , 35 , 202303120..

Menzel, H.; Weichart, B.; Schmidt, A.; Paul, S.; Knoll, W.; Stumpe, J.; Fischer, T. Small-angle X-ray scattering and ult raviolet-visible spectroscopy studies on the structure and structural changes in langmuir-blodgett films of polyglutamates with azobenzene moieties tethered by alkyl spacers of different length. Langmuir 2002 , 10 , 1926−1933..

Tong, X.; Cui, L.; Zhao, Y. Confinement effects on photoalignment, photochemical phase transition, and thermochromic behavior of liquid crystalline azobenzene-containing diblock copolymers. Macromolecules 2004 , 37 , 3101−3112..

Ishiba, K.; Morikawa, M. A.; Chikara, C.; Yamada, T.; Iwase, K.; Kawakita, M.; Kimizuka, N. Photoliquefiable ionic crystals: a phase crossover approach for photon energy storage materials with functional multiplicity. Angew. Chem. Int. Ed. 2014 , 54 , 1532−1536..

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Related Institution

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