Citation: Lei Li, Guang Yang, Tianbai Xiong, Tingzhu Duan, Jia Wang, Xin Wang. Metal-free click polymerization of thiols and chalcone-derived internal olefins in air to prepare functional clusteroluminescent polythioethers for dual-response fluorescent probe[J]. Chinese Chemical Letters, ;2025, 36(11): 111374. doi: 10.1016/j.cclet.2025.111374 shu

Metal-free click polymerization of thiols and chalcone-derived internal olefins in air to prepare functional clusteroluminescent polythioethers for dual-response fluorescent probe

Lei Li ^{a, b, 1} ,
Guang Yang ^{a, 1} ,
Tianbai Xiong ^b ,
Tingzhu Duan ^b ,
Jia Wang ^{b, *,} ,
Xin Wang ^{b, *,}

a.
College of Energy and Environmental Engineering, Hebei University of Engineering, Handan 056038, China
b.
Songshan Lake Materials Laboratory, Dongguan 523808, China

wangjia@sslab.org.cn

wangxin@sslab.org.cn

Received Date: 18 March 2025
Revised Date: 23 May 2025
Accepted Date: 26 May 2025
Available Online: 26 May 2025

Figures(4)

Thiol-ene click polymerization has become an effective synthetic tool for constructing diverse sulfur-containing polymers with advanced functions. However, the polymerization of internal alkene and thiol has been rarely used to prepare functional polymers because of large steric hindrance and relatively weak reactivity. In this work, a base-catalyzed click polymerization of thiols and internal olefins was successfully established in air. Notably, the polymerization went smoothly in halogen-containing solvent even without any catalyst via a radical step-growth polymerization. The polymerization enjoys excellent monomer applicability, which affords 16 well-defined polythioethers in high yields (up to 99%) with high molecular weights (M_w up to 19,600), good thermal stability (T_d,5% up to 326 ℃), broadly regulated glass transition temperatures (-24~95 ℃), and unconventional fluorescence. Via a simple solvent regulation strategy, the vanillin-derived polythioether could be used as a turn-off fluorescence probe for Fe³⁺ ions in DMF/H₂O and a turn-on probe for Ag⁺ ions in THF, with low detection limits of 9.15 × 10^–7 mol/L and 4.60 × 10^–7 mol/L, respectively. Additionally, the detection of Ag⁺ presented a transformation from a clear solution to an emulsion, expanding the application prospects through observing colorimetric and fluorescent dual signals. Thus, this work not only holds significance in establishing an efficient polymerization, but also provides a strategy to prepare sensitive fluorescent probes for multiple metal ions.
- Metal-free,
- Chalcone-derived,
- Click polymerization,
- Clusteroluminescence,
- Fluorescent probe
1. [1]
  N. Bayliss, B.V.K.J. Schmidt, Prog. Polym. Sci. 147 (2023) 101753. doi: 10.1016/j.progpolymsci.2023.101753
2. [2]
  S. Yang, Z. Liu, J. Membr. Sci. 222 (2003) 87–98. doi: 10.1016/S0376-7388(03)00220-5
3. [3]
  J. Wang, Z. Yue, J.S. Ince, J. Economy, J. Membr. Sci. 286 (2006) 333–341. doi: 10.1016/j.memsci.2006.10.022
4. [4]
  Z.H. Zhao, P.C. Zhao, S.Y. Chen, et al., Angew. Chem. Int. Ed. 62 (2023) e202301993. doi: 10.1002/anie.202301993
5. [5]
  Y. Hu, S.Y. Zhang, J.F. Xu, et al., Angew. Chem. Int. Ed. 62 (2023) e202312564. doi: 10.1002/anie.202312564
6. [6]
  L.P. Manker, M.A. Hedou, C. Broggi, et al., Nat. Sustain. 7 (2024) 640–651. doi: 10.1038/s41893-024-01298-7
7. [7]
  T. Lee, P.T. Dirlam, J.T. Njardarson, R.S. Glass, J. Pyun, J. Am. Chem. Soc. 144 (2022) 5–22. doi: 10.1021/jacs.1c09329
8. [8]
  Y.T. Zhou, Z.C. Zhu, K. Zhang, B. Yang, Macromol. Rapid Commun. 44 (2023) 2300411. doi: 10.1002/marc.202300411
9. [9]
  F.L. Zhao, Y. Li, W. Feng, Small Methods 2 (2018) 1800156. doi: 10.1002/smtd.201800156
10. [10]
  Y.N. Xia, X.C. Yue, Y. Sun, C.J. Zhang, X.H. Zhang, Angew. Chem. Int. Ed. 62 (2023) e202219251. doi: 10.1002/anie.202219251
11. [11]
  S. Wu, M. Luo, D.J. Darensbourg, X. Zuo, Macromolecules 52 (2019) 8596–8603. doi: 10.1021/acs.macromol.9b01811
12. [12]
  T.J. Yue, W.M. Ren, X.B. Lu, Chem. Rev. 123 (2023) 14038–14083. doi: 10.1021/acs.chemrev.3c00437
13. [13]
  W. Cao, F. Dai, R. Hu, B.Z. Tang, J. Am. Chem. Soc. 142 (2020) 978–986. doi: 10.1021/jacs.9b11066
14. [14]
  G. Feng, X. Feng, X. Liu, C. Zhang, X. Zhang, Macromolecules 57 (2024) 3757–3764. doi: 10.1021/acs.macromol.4c00303
15. [15]
  L. Xu, T. Zhou, M. Liao, R. Hu, B.Z. Tang, ACS Macro Lett. 8 (2019) 101–106. doi: 10.1021/acsmacrolett.8b00884
16. [16]
  M.T. Kwasny, C.M. Watkins, N.D. Posey, M.E. Matta, G.N. Tew, Macromolecules 51 (2018) 4280–4289. doi: 10.1021/acs.macromol.8b00334
17. [17]
  O. Daglar, U.S. Gunay, G. Hizal, U. Tunca, H. Durmaz, Macromolecules 52 (2019) 3558–3572. doi: 10.1021/acs.macromol.9b00293
18. [18]
  Y. Zhang, G. Chen, Y. Lin, et al., Polym. Chem. 6 (2015) 97–105. doi: 10.1039/C4PY01164C
19. [19]
  H. Feng, Y. Sheng, G. Chen, et al., CCS Chem. 6 (2024) 682–692. doi: 10.31635/ccschem.023.202303402
20. [20]
  O. Nuyken, T. Völkel, Makromol. Chem. Rapid Commun. 11 (1990) 365–373. doi: 10.1002/marc.1990.030110805
21. [21]
  N.B. Cramer, S.K. Reddy, A.K. O'Brien, C.N. Bowman, Macromolecules 36 (2003) 7964–7969. doi: 10.1021/ma034667s
22. [22]
  Z. Gao, Y. You, Q. Chen, M. North, H. Xie, Green Chem. 25 (2023) 172–182. doi: 10.1039/d2gc02901d
23. [23]
  B.W. Li, L.P. Wang, L. Gao, et al., Angew. Chem. Int. Ed. 63 (2024) e202400511. doi: 10.1002/anie.202400511
24. [24]
  J.W. Chan, C.E. Hoyle, A.B. Lowe, M. Bowman, Macromolecules 43 (2010) 6381–6388. doi: 10.1021/ma101069c
25. [25]
  O. Nuyken, T. Völkel, Makromol. Chem. 191 (1990) 2465–2473. doi: 10.1002/macp.1990.021911024
26. [26]
  R. Okutsu, Y. Suzuki, S. Ando, M. Ueda, Macromolecules 41 (2008) 6165–6168. doi: 10.1021/ma800797p
27. [27]
  J. Du, D. Huang, H. Li, et al., Macromolecules 53 (2020) 4932–4941. doi: 10.1021/acs.macromol.0c00311
28. [28]
  B. Li, X. Wang, D. Huang, et al., Chem. Sci. 39 (2023) 10718–10726. doi: 10.1039/d3sc03732k
29. [29]
  A. Rammohan, J.S. Reddy, G. Sravya, C.N. Rao, G.V. Zyryanov, Environ. Chem. Lett. 18 (2020) 433–458. doi: 10.1007/s10311-019-00959-w
30. [30]
  B.X. Li, B.W. Feng, J. Wang, Y.S. Qin, Luminescence 39 (2024) e4630. doi: 10.1002/bio.4630
31. [31]
  H. Zhang, B.Z. Tang, JACS Au 1 (2021) 1805–1814. doi: 10.1021/jacsau.1c00311
32. [32]
  Z.T. Zhang, Z.P. Xiong, B. Chu, et al., Aggregate 3 (2022) e278. doi: 10.1002/agt2.278
33. [33]
  K.P. Carter, A.M. Young, A.E. Palmer, Chem. Rev. 114 (2014) 4564–4601. doi: 10.1021/cr400546e
34. [34]
  Y.J. Huang, W.C. Zhao, X. Zhang, H. Peng Y.F. Gong, Chem. Eng. J. 375 (2019) 121935. doi: 10.1016/j.cej.2019.121935
35. [35]
  H.N. Xiang, J.P. Wang, Z.H. Guo, et al., Angew. Chem. Int. Ed. 62 (2023) e202313779. doi: 10.1002/anie.202313779
36. [36]
  R.C. Hider, X. Kong, Dalton Trans. 42 (2013) 3220–3229. doi: 10.1039/C2DT32149A
37. [37]
  Y. Feng, T. Bai, H. Yan, et al., Macromolecules 52 (2019) 3075–3082. doi: 10.1021/acs.macromol.9b00263
38. [38]
  J. Wang, M. Li, L. Xu, et al., Macromolecules 57 (2024) 122–131. doi: 10.1021/acs.macromol.3c02132
39. [39]
  J. Wang, T. Tian, R. Zhang, et al., J. Am. Chem. Soc. 146 (2024) 6652–6664. doi: 10.1021/jacs.3c12588
40. [40]
  A. Saha, W. Ali, D.B. Werz, D. Maiti, Nat. Commun. 14 (2023) 8173. doi: 10.1038/s41467-023-43286-z
1. [1]
  Chunhua Ma , Mengjiao Liu , Siyu Ouyang , Zhenwei Cui , Jingjing Bi , Yuqin Jiang , Zhiguo Zhang . Metal-free construction of diverse 1,2,4-triazolo[1,5-a]pyridines on water. Chinese Chemical Letters, 2025, 36(1): 109755-. doi: 10.1016/j.cclet.2024.109755
2. [2]
  Yudi Cheng , Xiao Wang , Jiao Chen , Zihan Zhang , Jiadong Ou , Mengyao She , Fulin Chen , Jianli Li . A near-infrared fluorescent probe for visualizing transformation pathway of Cys/Hcy and H₂S and its applications in living system. Chinese Chemical Letters, 2024, 35(5): 109156-. doi: 10.1016/j.cclet.2023.109156
3. [3]
  Chuan-Zhi Ni , Ruo-Ming Li , Fang-Qi Zhang , Qu-Ao-Wei Li , Yuan-Yuan Zhu , Jie Zeng , Shuang-Xi Gu . A chiral fluorescent probe for molecular recognition of basic amino acids in solutions and cells. Chinese Chemical Letters, 2024, 35(10): 109862-. doi: 10.1016/j.cclet.2024.109862
4. [4]
  Tao Liu , Xuwei Han , Xueyi Sun , Weijie Zhang , Ke Gao , Runan Min , Yuting Tian , Caixia Yin . An activated fluorescent probe to monitor NO fluctuation in Parkinson’s disease. Chinese Chemical Letters, 2025, 36(3): 110170-. doi: 10.1016/j.cclet.2024.110170
5. [5]
  Qian Pang , Fangjun Huo , Yongkang Yue , Caixia Yin . ONOO⁻ and viscosity dual-response fluorescent probe for arthritis imaging in vivo. Chinese Chemical Letters, 2025, 36(9): 110713-. doi: 10.1016/j.cclet.2024.110713
6. [6]
  Huamei Zhang , Jingjing Liu , Mingyue Li , Shida Ma , Xucong Zhou , Aixia Meng , Weina Han , Jin Zhou . Imaging polarity changes in pneumonia and lung cancer using a lipid droplet-targeted near-infrared fluorescent probe. Chinese Chemical Letters, 2024, 35(12): 110020-. doi: 10.1016/j.cclet.2024.110020
7. [7]
  Fan Zheng , Runsha Xiao , Shuai Huang , Zhikang Chen , Chen Lai , Anyao Bi , Heying Yao , Xueping Feng , Zihua Chen , Wenbin Zeng . Accurate visualization colorectal cancer by monitoring viscosity variations with a novel mitochondria-targeted fluorescent probe. Chinese Chemical Letters, 2025, 36(2): 109876-. doi: 10.1016/j.cclet.2024.109876
8. [8]
  Zhixiao Xiong , Shanni Qiu , Yuyu Wang , Houna Duan , Yi Xiao , Yufang Xu , Weiping Zhu , Xuhong Qian . Photocalibrated NO release from the zinc ion fluorescent probe based on naphthalimide and its application in living cells. Chinese Chemical Letters, 2025, 36(4): 110002-. doi: 10.1016/j.cclet.2024.110002
9. [9]
  Jiayu Zeng , Minhui Liu , Ting Yang , Jia Huang , Songjiao Li , Wanting Zhang , Dan Cheng , Longwei He , Jia Zhou . Two-dimensional design strategy to construct smart dual-responsive fluorescent probe for the precise tracking of ischemic stroke. Chinese Chemical Letters, 2025, 36(5): 110166-. doi: 10.1016/j.cclet.2024.110166
10. [10]
  Xianzhu Luo , Feifei Yu , Rui Wang , Tian Su , Pan Luo , Pengfei Wen , Fabiao Yu . A near-infrared two-photon fluorescent probe for the detection of HClO in inflammatory and tumor-bearing mice. Chinese Chemical Letters, 2025, 36(7): 110531-. doi: 10.1016/j.cclet.2024.110531
11. [11]
  Xinyi Zhao , Yuai Duan , Zihan Liu , Hua Geng , Yaping Li , Zhongfeng Li , Tianyu Han . Mapping sweat pores for biometric identification based on a donor-acceptor hydrophilic fluorescent probe. Chinese Chemical Letters, 2025, 36(8): 110617-. doi: 10.1016/j.cclet.2024.110617
12. [12]
  Chuanfeng Fan , Jian Gao , Yingkai Gao , Xintong Yang , Gaoning Li , Xiaochun Wang , Fei Li , Jin Zhou , Haifeng Yu , Yi Huang , Jin Chen , Yingying Shan , Li Chen . A non-peptide-based chymotrypsin-targeted long-wavelength emission fluorescent probe with large Stokes shift and its application in bioimaging. Chinese Chemical Letters, 2024, 35(10): 109838-. doi: 10.1016/j.cclet.2024.109838
13. [13]
  Lei Shen , Hongmei Liu , Ming Jin , Jinchao Zhang , Caixia Yin , Shuxiang Wang , Yutao Yang . “Three-in-one” strategy of trifluoromethyl regulated blood-brain barrier permeable fluorescent probe for peroxynitrite and antiepileptic evaluation of edaravone. Chinese Chemical Letters, 2024, 35(10): 109572-. doi: 10.1016/j.cclet.2024.109572
14. [14]
  Han-Min Wang , Yan-Chen Li , Lu-Lu Sun , Ming-Ye Tang , Jia Liu , Jiahao Cai , Lei Dong , Jia Li , Yi Zang , Hai-Hao Han , Xiao-Peng He . Protein-encapsulated long-wavelength fluorescent probe hybrid for imaging lipid droplets in living cells and mice with non-alcoholic fatty liver. Chinese Chemical Letters, 2024, 35(11): 109603-. doi: 10.1016/j.cclet.2024.109603
15. [15]
  Wenping Dong , Mo Ma , Jingkang Li , Lanlan Xu , Dejiang Gao , Pinyi Ma , Daqian Song . Near-infrared fluorescent probe with large Stokes shift and long emission wavelength for rapid diagnosis of lung cancer via aerosol inhalation delivery. Chinese Chemical Letters, 2025, 36(5): 110147-. doi: 10.1016/j.cclet.2024.110147
16. [16]
  Meiling Zhao , Yao Lu , Yutao Zhang , Haoyun Xue , Zhiqian Guo . Ultra-high signal-to-noise ratio near-infrared chemiluminescent probe for in vivo sensing singlet oxygen. Chinese Chemical Letters, 2025, 36(5): 110105-. doi: 10.1016/j.cclet.2024.110105
17. [17]
  Tong Li , Leping Pan , Yan Zhang , Jihu Su , Kai Li , Kuiliang Li , Hu Chen , Qi Sun , Zhiyong Wang . Electrochemical construction of 2,5-diaryloxazoles via N–H and C(sp³)-H functionalization. Chinese Chemical Letters, 2024, 35(4): 108897-. doi: 10.1016/j.cclet.2023.108897
18. [18]
  Hefei Yang , Le-Cheng Wang , Xiao-Feng Wu . Sustainable carbonylative transformation of alkyl iodides to amides via crosslinking of EDA and XAT. Chinese Chemical Letters, 2025, 36(9): 110843-. doi: 10.1016/j.cclet.2025.110843
19. [19]
  Jiajia Lv , Jie Gao , Hongyu Li , Zeli Yuan , Nan Dong . Rational design of hydroxytricyanopyrrole-based probes with high affinity and rapid visualization for amyloid-β aggregates in vitro and in vivo. Chinese Chemical Letters, 2024, 35(5): 108940-. doi: 10.1016/j.cclet.2023.108940
20. [20]
  Chao Liu , Chao Jia , Shi-Xian Gan , Qiao-Yan Qi , Guo-Fang Jiang , Xin Zhao . A luminescent one-dimensional covalent organic framework for organic arsenic sensing in water. Chinese Chemical Letters, 2024, 35(11): 109750-. doi: 10.1016/j.cclet.2024.109750

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(22)
HTML views(2)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142