Citation: Xiaojian Yan, Saijin Huang, Wenfeng Liu, Li-Li Tan, Gaobin Wang, Liping Cao, Li Shang. Tungsten oxide quantum dot-based supramolecular assembly with tunable photochromic kinetics towards time-encoded anti-counterfeiting[J]. Chinese Chemical Letters, ;2026, 37(3): 111427. doi: 10.1016/j.cclet.2025.111427 shu

Tungsten oxide quantum dot-based supramolecular assembly with tunable photochromic kinetics towards time-encoded anti-counterfeiting

Xiaojian Yan ^{a, b} ,
Saijin Huang ^b ,
Wenfeng Liu ^b ,
Li-Li Tan ^b ,
Gaobin Wang ^c ,
Liping Cao ^d ,
Li Shang ^{a, b, *,}

a.
Shenzhen Research Institute of Northwestern Polytechnical University, Shenzhen 518057, China
b.
State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an 710072, China
c.
Queen Mary University of London Engineering School, Northwestern Polytechnical University, Xi'an 710072, China
d.
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, China

li.shang@nwpu.edu.cn

Received Date: 28 March 2025
Revised Date: 15 May 2025
Accepted Date: 6 June 2025
Available Online: 7 June 2025

Figures(7)

The development of advanced anti-counterfeiting technology using photochromic inorganic materials with dynamic optical signals has garnered significant interest, but the limited color response and un-controlled photochromic kinetics largely restrict their practical application. In this work, we report the design of photochromic supramolecular assembly based on host-guest chemistry, enabling kinetics-tunable time-encoded anti-counterfeiting. By co-assembling of photochromic tungsten oxide quantum dots (WO₃ QDs) with cucurbit[7]uril (CB[7]), we developed a kinetics-tunable photochromic supramolecular assembly (WO₃CB[7]). The WO₃CB[7] assembly exhibits distinct photochromic kinetics compared to free WO₃ QDs due to efficient suppression of photogenerated decomposition of water adsorbed on WO₃ QDs, as verified by spectral and photophysical analysis. The photochromic kinetics can be readily modulated by adjusting the WO₃ QDs to CB[7] ratio. The kinetics-tunable photochromic WO₃CB[7] assembly has been successfully applied as innovative anti-counterfeiting materials for fabricating time-encoded anti-counterfeiting arrays and information encryption system. The irradiation time serves as a key parameter for decrypting the final information, thereby enhancing the complexity of replication and counterfeiting. This approach offers a simple, scalable and generalizable strategy for designing advanced optical anti-counterfeiting materials by integrating inorganic photochromic materials with the supramolecular strategy.
- Tungsten oxide quantum dots,
- Anti-counterfeiting,
- Photochromic kinetics,
- Supramolecular assembly
1. [1]
  Z.H. Zuo, Z.W. Feng, Y.Y. Peng, et al., ACS Nano 18 (2024) 4456–4466. doi: 10.1021/acsnano.3c11092
2. [2]
  A. Abdollahi, H. Roghani-Mamaqani, B. Razavi, Prog. Polym. Sci. 98 (2019) 101149. doi: 10.1016/j.progpolymsci.2019.101149
3. [3]
  J.R. Otaegui, D. Ruiz-Molina, J. Hernando, C. Roscini, Adv. Funct. Mater. 34 (2024) 2402510. doi: 10.1002/adfm.202402510
4. [4]
  T. Lin, C. Tian, Y. Sun, et al., Chin. Chem. Lett. 34 (2023) 107864. doi: 10.1016/j.cclet.2022.107864
5. [5]
  B. Wu, M. Si, L. Hua, et al., Adv. Mater. 36 (2024) 2401659. doi: 10.1002/adma.202401659
6. [6]
  A. Abdollahi, H. Roghani-Mamaqani, B. Razavi, M. Salami-Kalajahi, ACS Nano 14 (2020) 14417–14492. doi: 10.1021/acsnano.0c07289
7. [7]
  W. Zhong, L. Shang, Chem. Sci. 2024 (2024) 6218–6228. doi: 10.1039/d4sc00114a
8. [8]
  G. Liu, Y. Li, C. Tian, et al., Chin. Chem. Lett. 35 (2024) 109403. doi: 10.1016/j.cclet.2023.109403
9. [9]
  H. Li, X. Peng, W. Xi, et al., Adv. Funct. Mater. 34 (2024) 2405877. doi: 10.1002/adfm.202405877
10. [10]
  T. Chen, B. Xu, J. Han, et al., ACS Appl. Mater. Interfaces 16 (2024) 13305–13315. doi: 10.1021/acsami.3c19129
11. [11]
  L. Wang, W. Zhong, W. Gao, W. Liu, L. Shang, Chem. Eng. J. 479 (2024) 147490. doi: 10.1016/j.cej.2023.147490
12. [12]
  T. Zhang, X.Y. Lou, X. Li, et al., Adv. Mater. 35 (2023) 2210551. doi: 10.1002/adma.202210551
13. [13]
  T. Wu, Y. Tian, J. Wu, et al., Dyes Pigment. 212 (2023) 111119. doi: 10.1016/j.dyepig.2023.111119
14. [14]
  Z. Wang, Z. Ding, Y. Yang, et al., Chem. Eng. J. 457 (2023) 141293. doi: 10.1016/j.cej.2023.141293
15. [15]
  H. Wang, J. Tang, H. Deng, et al., J. Mater. Chem. C 11 (2023) 15945–15951. doi: 10.1039/d3tc03322h
16. [16]
  X. Le, H. Shang, S. Wu, et al., Adv. Funct. Mater. 31 (2021) 2108365. doi: 10.1002/adfm.202108365
17. [17]
  J. Du, Z. Yang, H. Lin, D. Poelman, Responsive Mater. 2 (2024) e20240004. doi: 10.1002/rpm.20240004
18. [18]
  X. Dong, Y. Dang, Z. Wu, et al., Mater. Today Energy 44 (2024) 101632. doi: 10.1016/j.mtener.2024.101632
19. [19]
  A.B.A. Kayani, S. Kuriakose, M. Monshipouri, et al., Small. 17 (2021) 2100621. doi: 10.1002/smll.202100621
20. [20]
  D. Wei, Y. Zhang, W. Xue, et al., ACS Sustain. Chem. Eng. 12 (2024) 6310–6319. doi: 10.1021/acssuschemeng.4c00067
21. [21]
  B. Cui, G. Fu, Appl. Surf. Sci. 655 (2024) 159520. doi: 10.1016/j.apsusc.2024.159520
22. [22]
  W. Si, S. Wang, Z. Yu, et al., Chem. Eng. J. 492 (2024) 152232. doi: 10.1016/j.cej.2024.152232
23. [23]
  X. Yan, W. Zhong, S. Qu, Z. Li, L. Shang, J. Colloid Interface Sci. 646 (2023) 855–862. doi: 10.1016/j.jcis.2023.05.033
24. [24]
  T. Chen, X. Mai, Y. Li, et al., Chem. Eng. J. 499 (2024) 155999. doi: 10.1016/j.cej.2024.155999
25. [25]
  W. Tang, C. Zuo, C. Ma, et al., J. Mater. Chem. C 10 (2022) 18375–18384. doi: 10.1039/d2tc04137e
26. [26]
  S.W. Feng, X.L. Peng, J.J. Cui, et al., Adv. Funct. Mater. 34 (2024) 2401431. doi: 10.1002/adfm.202401431
27. [27]
  X. Zhang, R. Yang, Y. Dong, et al., Angew. Chem. Int. Ed. 63 (2024) e202403973. doi: 10.1002/anie.202403973
28. [28]
  D. Das, P. Das, T. Das, et al., Angew. Chem. Int. Ed. (2024) e202414239.
29. [29]
  G. Zhao, Y. Kou, N. Song, et al., ACS Nano 17 (2023) 7624–7635. doi: 10.1021/acsnano.3c00074
30. [30]
  Y.Y. Gao, Y.H. Yang, Y.H. Wei, et al., Adv. Funct. Mater. (2024) 2416025.
31. [31]
  X. Yan, L. Wang, W. Zhong, et al., Nano Res. 18 (2025) 94907172. doi: 10.26599/nr.2025.94907172
32. [32]
  F. Tong, Y. Zhou, Y. Xu, et al., Exploration 3 (2023) 20210111. doi: 10.1002/EXP.20210111
33. [33]
  H. Yang, S. Li, J. Zheng, et al., Adv. Mater. 35 (2023) 2301300. doi: 10.1002/adma.202301300
34. [34]
  Y. Zhang, Y. Ding, F. Lan, et al., Nanoscale 16 (2024) 21279–21293. doi: 10.1039/d4nr03781b
35. [35]
  S. Wang, W. Fan, Z. Liu, A. Yu, X. Jiang, J. Mater. Chem. C 6 (2018) 191–212. doi: 10.1039/C7TC04189F
36. [36]
  W. Meng, A.J.J. Kragt, X. Hu, et al., Adv. Funct. Mater. 34 (2024) 2402494. doi: 10.1002/adfm.202402494
37. [37]
  M. Chen, X. Zhang, W. Sun, et al., Nano Energy 123 (2024) 109352. doi: 10.1016/j.nanoen.2024.109352
38. [38]
  W. Meng, A.J.J. Kragt, Y. Gao, et al., Adv. Mater. 36 (2023) 2304910.
39. [39]
  Y. Zhu, Y. Yao, Z. Chen, et al., Sol. Energ. Mat. Sol. C 239 (2022) 111664. doi: 10.1016/j.solmat.2022.111664
40. [40]
  Q. Liu, C. Hu, X. Wang, Appl. Surf. Sci. 480 (2019) 404–409. doi: 10.1016/j.apsusc.2019.02.097
41. [41]
  D. Kim, A. Aktalay, N. Jensen, et al., J. Am. Chem. Soc. 144 (2022) 14235–14247. doi: 10.1021/jacs.2c05036
42. [42]
  W.L. Zhou, W. Lin, Y. Chen, X.Y. Dai, Y. Liu, Small 19 (2023) 2304009. doi: 10.1002/smll.202304009
43. [43]
  B. Zhao, M. Wei, X. Zhou, et al., Adv. Funct. Mater. 35 (2025) 2416011. doi: 10.1002/adfm.202416011
44. [44]
  W. Zhong, X. Yan, S. Qu, L. Shang, Aggregate 4 (2023) e245. doi: 10.1002/agt2.245
45. [45]
  A. Syal, D. Sud, Sens. Actuator B: Chem. 266 (2018) 1–8.
46. [46]
  M.H. Gehlen, J. Photochem. Photobiol. C: Photochem. Rev. 42 (2020) 100338. doi: 10.1016/j.jphotochemrev.2019.100338
47. [47]
  L.L. Tan, M. Wei, L. Shang, Y.W. Yang, Adv. Funct. Mater. 31 (2021) 2007277. doi: 10.1002/adfm.202007277
48. [48]
  D. Li, Z.F. Feng, Y.J. Han, et al., Adv. Sci. 9 (2022) 2104790. doi: 10.1002/advs.202104790
49. [49]
  Y.W. Li, Q.F. Li, X.R. Miao, et al., Angew. Chem. Int. Ed. 60 (2021) 6744–6751. doi: 10.1002/anie.202012681
50. [50]
  Y.Z. Zhang, B. Zhou, Y.X. Liu, et al., J. Fluoresc. 18 (2008) 109–118. doi: 10.1007/s10895-007-0247-4
51. [51]
  M. Li, R. Yang, X. Feng, et al., Food Hydrocoll. 127 (2022) 107506. doi: 10.1016/j.foodhyd.2022.107506
52. [52]
  S.B. Black, Y. Chang, C. Bae, M.A. Hickner, J. Phys. Chem. B 117 (2013) 16266–16274. doi: 10.1021/jp406242h
53. [53]
  Y. Huang, B. Wang, P. Lyu, et al., Nano Res. 16 (2023) 12165–12172. doi: 10.1007/s12274-023-5600-7
54. [54]
  B.B. Cui, C.P. Guo, Z.H. Zhang, G.D. Fu, Chem. Eng. J. 455 (2023) 140822. doi: 10.1016/j.cej.2022.140822
55. [55]
  K. Manalastas-Cantos, P.V. Konarev, N.R. Hajizadeh, et al., J. Appl. Crystallogr. 54 (2021) 343–355. doi: 10.1107/s1600576720013412
56. [56]
  X. Zuo, D.M. Tiede, J. Appl. Crystallogr. 57 (2024) 1446–1455. doi: 10.1107/s1600576724007222
57. [57]
  H. Liu, P.H. Zwart, J. Struct. Biol. 180 (2012) 226–234. doi: 10.1016/j.jsb.2012.05.011
58. [58]
  J. Eberhardt, D. Santos-Martins, A.F. Tillack, S. Forli, J. Chem. Inf. Model. 61 (2021) 3891–3898. doi: 10.1021/acs.jcim.1c00203
59. [59]
  R.E. Rigsby, A.B. Parker, Biochem. Mol. Biol. Educ. 44 (2016) 433–437. doi: 10.1002/bmb.20966
60. [60]
  J. Tian, L. Xia, J. Wu, et al., ACS Appl. Mater. Interfaces 12 (2020) 32352–32359. doi: 10.1021/acsami.0c07333
61. [61]
  W. Zhao, B. Qiao, J. Tropp, et al., J. Am. Chem. Soc. 141 (2019) 4980–4989. doi: 10.1021/jacs.9b00248
62. [62]
  S. Yamazaki, K. Isoyama, Langmuir 39 (2023) 10240–10248. doi: 10.1021/acs.langmuir.3c01227
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