Citation: Xing-yu Wu, Jin Ming, Jian-chao Xie, De-cheng Wan, Malval Jean Pierre. Effects of Conjugated Systems on UV-Visible Light-sensitive D-π-A Type Sulfonium Salt Photoacid Generators[J]. Chinese Journal of Polymer Science, ;2016, 34(12): 1456-1468. doi: 10.1007/s10118-016-1863-8 shu

Effects of Conjugated Systems on UV-Visible Light-sensitive D-π-A Type Sulfonium Salt Photoacid Generators

a.
School of Materials Science and Engineering, Tongji University, Shanghai 201804, China
b.
Institut de Science des Matériaux de Mulhouse, UMR CNRS 7361, Université de Haute-Alsace, 15 rue Jean Starcky, 68057 Mulhouse, France

Corresponding author: Jin Ming, mingjin@tongji.edu.cn
Received Date: 24 June 2016
Revised Date: 12 August 2016
Accepted Date: 12 August 2016

Fund Project: the National Natural Science Foundation of China 51173134the National Natural Science Foundation of China 51573139Fundamental Research Funds for the Central Universities and the Open Measuring Fund for Large Instrument and Equipment of Tongji University 0002015033

A series of D-π-A type sulfonium salt photoacid generators with different π-conjugated structures, such as triphenyl, phenylstilbene, styryl-biphenyl, and stilbene, were designed to determine the effect of molecular structures on the photochemical and photophysical properties. The mechanisms of photochemical generation of H⁺ were studied by UV-Vis spectroscopy, theoretical calculations, and fluorescence spectroscopy. It is found that the frontier orbits determine the absorption, the molar extinction coefficients, and the quantum yields of photoacid generation. Triphenyl systems connected with sulfonium are beneficial to increase the quantum yields of acid generation. The photoreactivity of four sulfonium salts was further evaluated through the polymerizations of various epoxide monomers at different irradiation wavelengths (365-425 nm) by using the real-time infrared spectroscopy with light-emitting diodes. The high quantum yields for acid generation (Φ_H⁺=~0.32 to 0.58) and the high molar extinction coefficients (ε=~23500 L·mol^-1·cm^-1 to 31000 L·mol^-1·cm^-1) of the sulfonium salts lead to high conversion rates (over 50%-80%). Hence, these photoinitiators exhibit potential for the photocuring applications.
- Sulfonium salt,
- Photoacid generators,
- π-conjugated structures
1. [1]
  Crivello, J.V. and Lam, J.H.W., Macromolecules, 1977, 10(6):1307 doi: 10.1021/ma60060a028
2. [2]
  Beak, P. and Sullivan, T.A., J. Am. Chem. Soc., 1982, 104(16):4450 doi: 10.1021/ja00380a020
3. [3]
  Saeva, F.D. and Morgan, B.P., J. Am. Chem. Soc., 1984, 106(15):4121 doi: 10.1021/ja00327a010
4. [4]
  Fouassier, J.P. and Lalevée, J., "Photoinitiator for polymer synthesis-scope, reactivity, and efficiency", Wiley-VCH Berlag GmbH & Co. KGaA, Weinheim, 2012
5. [5]
  Davidson, S., "Exploring the science, technology and application of UV and EB curing", Sita Technolgy Ltd, London, 1999
6. [6]
  Fouassier, J.P., "Photoinitiator, photopolymerization and photocuring:fundamentals and applications", Hanser Publishers, New York, 1995
7. [7]
  Cordon, C. and Miller, C., "UV-LED:presented by RadTech-the association for UV & EB technology", RadTech International, Bethesda, 2013
8. [8]
  Liu, G., Zhu, X., Xu, B., Qian, X., Song, G. and Nie, J., J. Appl. Polym. Sci., 2013, 130(5):3698 doi: 10.1002/app.39612
9. [9]
  Sui, X., Feng, X., di Luca, A., van Blitterswijk, C.A., Moroni, L., Hempenius, M.A. and Vancso, G.J., Polym. Chem., 2013, 4(2):337 doi: 10.1039/C2PY20431B
10. [10]
  Tehfe, M.A., Dumur, F., Graff, B., Morlet-Savary, F., Fouassier, J.P., Gigmes, D. and Lalevée, J., Macromolecules, 2012, 45(21):8639 doi: 10.1021/ma301931p
11. [11]
  Walsh, Z., Levkin, P.A., Jain, V., Paull, B., Svec, F. and Macka, M., J. Sep. Sci., 2010, 33(1):61 doi: 10.1002/jssc.v33:1
12. [12]
  Xiao, P., Frigoli, M., Dumur, F., Graff, B., Gigmes, D., Fouassier, J.P. and Lalevée, J., Macromolecules, 2014, 47(1):106 doi: 10.1021/ma402196p
13. [13]
  Dietlin, C., Schweizer, S., Xiao, P., Zhang, J., Morlet-Savary, F., Graff, B., Fouassier, J.P. and Lalevée, J., Polym. Chem., 2015, 6(21):3895 doi: 10.1039/C5PY00258C
14. [14]
  Tehfe, M.A., Dumur, F., Xiao, P., Delgove, M., Graff, B., Fouassier, J.P., Gigmes, D. and Lalevée, J., Polym. Chem., 2014, 5(2):382 doi: 10.1039/C3PY00922J
15. [15]
  Xiao, P., Hong, W., Li, Y., Dumur, F., Graff, B., Fouassier, J.P., Gigmes, D. and Lalevée, J., Polym. Chem., 2014, 5(7):2293 doi: 10.1039/c3py01599h
16. [16]
  Zhang, J., Zivic, N., Dumur, F., Xiao, P., Graff, B., Gigmes, D., Fouassier, J.P. and Lalevée, J., J. Polym. Sci., Part A:Polym. Chem., 2015, 53(3):445 doi: 10.1002/pola.v53.3
17. [17]
  Saeva, F.D., Garcia, E. and Martic, P.A., J. Photochem. Photobiol. A-Chem., 1995, 86(1-3):149 doi: 10.1016/1010-6030(94)03923-I
18. [18]
  Zhou, W.H., Kuebler, S.M., Braun, K.L., Yu, T.Y., Cammack, J.K., Ober, C.K., Perry, J.W. and Marder, S.R., Science, 2002, 296(5570):1106 doi: 10.1126/science.296.5570.1106
19. [19]
  Yanez, C.O., Andrade, C.D. and Belfield, K.D., Chem. Commun., 2009, 0(7):827
20. [20]
  Xia, R., Malval, J.P., Jin, M., Spangenberg, A., Wan, D., Pu, H., Vergote, T., Morlet-Savary, F., Chaumeil, H., Baldeck, P., Poizat, O. and Soppera, O., Chem. Mater., 2012, 24(2):237 doi: 10.1021/cm2030075
21. [21]
  Jin, M., Hong, H., Xie, J., Malval, J.P., Spangenberg, A., Soppera, O., Wan, D., Pu, H., Versace, D.L., Leclerc, T., Baldeck, P., Poizat, O. and Knopf, S., Polym. Chem., 2014, 5(16):4747 doi: 10.1039/C4PY00424H
22. [22]
  De Waele, V., Hamm, M., Vergote, T., Chaumeil, H., Jin, M., Malval, J.P., Baldeck, P. and Poizat, O., Chem. Mater., 2015, 27(5):1684 doi: 10.1021/cm504474g
23. [23]
  Jin, M., Wu, X., Xie, J., Malval, J.P. and Wan, D., RSC Adv., 2015, 5(68):55340 doi: 10.1039/C5RA11350D
24. [24]
  Saeva, F.D., Breslin, D.T. and Luss, H.R., J. Am. Chem. Soc., 1991, 113(14):5333 doi: 10.1021/ja00014a028
25. [25]
  Zhou, W., Kuebler, S.M., Carrig, D., Perry, J.W. and Marder, S.R., J. Am. Chem. Soc., 2002, 124(9):1897 doi: 10.1021/ja011186k
26. [26]
  Pohlers, G., Scaiano, J.C. and Sinta, R., Chem. Mater., 1997, 9(12):3222 doi: 10.1021/cm970587p
27. [27]
  Frisch, M.J., "Gaussian 09, Revision B.01.", Gaussian Inc, Wallingford, 2009
28. [28]
  Fang, B., Jin, M., Wu, X., Zhang, Y. and Wan, D., Dyes Pigment., 2016, 126:54 doi: 10.1016/j.dyepig.2015.11.012
29. [29]
  Jin, M., Xie, J., Malval, J.P., Spangenberg, A., Soppera, O., Versace, D.L., Leclerc, T., Pan, H., Wan, D., Pu, H., Baldeck, P., Poizat, O. and Knopf, S., J. Mater. Chem. C, 2014, 2(35):7201 doi: 10.1039/C4TC00706A
30. [30]
  Jin, M., Xu, H., Hong, H., Malval, J.P., Zhang, Y., Ren, A., Wan, D. and Pu, H., Chem. Commun., 2013, 49(76):8480 doi: 10.1039/c3cc43018a
31. [31]
  Zhou, W.H., Kuebler, S.M., Carrig, D., Perry, J.W. and Marder, S.R., J. Am. Chem. Soc., 2002, 124(9):1897 doi: 10.1021/ja011186k
32. [32]
  Saeva, F.D., Breslin, D.T. and Luss, H.R., J. Am. Chem. Soc., 1991, 113(14):5333 doi: 10.1021/ja00014a028
33. [33]
  Wang, X.Z., Saeva, F.D. and Kampmeier, J.A., J. Am. Chem. Soc., 1999, 121(18):4364 doi: 10.1021/ja982932x
34. [34]
  Park, J., Kihara, N., Ikeda, T. and Endo, T., Macromolecules, 1997, 30(11):3414 doi: 10.1021/ma9610222
35. [35]
  Kuebler, S.M., Braun, K.L., Zhou, W., Cammack, J.K., Yu, T., Ober, C.K., Marder, S.R. and Perry, J.W., J. Photochem. Photobiol., A, 2003, 158(2-3):163 doi: 10.1016/S1010-6030(03)00030-3
36. [36]
  Yagci, Y., Jockusch, S. and Turro, N.J., Macromolecules, 2010, 43(15):6245 doi: 10.1021/ma1007545
37. [37]
  Tehfe, M.A., Dumur, F., Contal, E., Graff, B., Morlet-Savary, F., Gigmes, D., Fouassier, J.P. and Lalevée, J., Polym. Chem., 2013, 4(5):1625 doi: 10.1039/C2PY20950K
38. [38]
  Tehfe, M.A., Lalevée, J., Morlet-Savary, F., Graff, B., Blanchard, N. and Fouassier, J.P., ACS Macro Lett., 2011, 1(1):198
1. [1]
  Junxin Li , Chao Chen , Yuzhen Dong , Jian Lv , Jun-Mei Peng , Yuan-Ye Jiang , Daoshan Yang . Ligand-promoted reductive coupling between aryl iodides and cyclic sulfonium salts by nickel catalysis. Chinese Chemical Letters, 2024, 35(11): 109732-. doi: 10.1016/j.cclet.2024.109732
2. [2]
  Rong-Nan Yi , Wei-Min He . Visible light/copper catalysis enabled radial type ring-opening of sulfonium salts. Chinese Chemical Letters, 2025, 36(4): 110787-. doi: 10.1016/j.cclet.2024.110787
3. [3]
  Qiangwei Wang , Huijiao Liu , Mengjie Wang , Haojie Zhang , Jianda Xie , Xuanwei Hu , Shiming Zhou , Weitai Wu . Observation of high ionic conductivity of polyelectrolyte microgels in salt-free solutions. Chinese Chemical Letters, 2024, 35(4): 108743-. doi: 10.1016/j.cclet.2023.108743
4. [4]
  Kailong Zhang , Chao Zhang , Luanhui Wu , Qidong Yang , Jiadong Zhang , Guang Hu , Liang Song , Gaoran Li , Wenlong Cai . Chloride molten salt derived attapulgite with ground-breaking electrochemical performance. Chinese Chemical Letters, 2024, 35(10): 109618-. doi: 10.1016/j.cclet.2024.109618
5. [5]
  Junhan Luo , Qi Qing , Liqin Huang , Zhe Wang , Shuang Liu , Jing Chen , Yuexiang Lu . Non-contact gaseous microplasma electrode as anode for electrodeposition of metal and metal alloy in molten salt. Chinese Chemical Letters, 2024, 35(4): 108483-. doi: 10.1016/j.cclet.2023.108483
6. [6]
  Kuan Deng , Fei Yang , Zhi-Qi Cheng , Bi-Wen Ren , Hua Liu , Jiao Chen , Meng-Yao She , Le Yu , Xiao-Gang Liu , Hai-Tao Feng , Jian-Li Li . Construction of wavelength-tunable DSE quinoline salt derivatives by regulating the hybridization form of the nitrogen atom and intramolecular torsion angle. Chinese Chemical Letters, 2024, 35(10): 109464-. doi: 10.1016/j.cclet.2023.109464
7. [7]
  Jiao Wang , Shuang-Yan Lang , Zhen-Zhen Shen , Gui-Xian Liu , Jian-Xin Tian , Yuan Li , Rui-Zhi Liu , Rui Wen . In situ imaging of the interfacial processes manipulated by salt concentration on zinc anodes in zinc metal batteries. Chinese Chemical Letters, 2025, 36(4): 109815-. doi: 10.1016/j.cclet.2024.109815
8. [8]
  Zhenyang Lin . A classification scheme for inorganic cluster compounds based on their electronic structures and bonding characteristics. Chinese Journal of Structural Chemistry, 2024, 43(5): 100254-100254. doi: 10.1016/j.cjsc.2024.100254
9. [9]
  Jiale Zheng , Mei Chen , Huadong Yuan , Jianmin Luo , Yao Wang , Jianwei Nai , Xinyong Tao , Yujing Liu . Electron-microscopical visualization on the interfacial and crystallographic structures of lithium metal anode. Chinese Chemical Letters, 2024, 35(6): 108812-. doi: 10.1016/j.cclet.2023.108812
10. [10]
  Luyao Lu , Chen Zhu , Fei Li , Pu Wang , Xi Kang , Yong Pei , Manzhou Zhu . Ligand effects on geometric structures and catalytic activities of atomically precise copper nanoclusters. Chinese Journal of Structural Chemistry, 2024, 43(10): 100411-100411. doi: 10.1016/j.cjsc.2024.100411
11. [11]
  Xiumei LI , Yanju HUANG , Bo LIU , Yaru PAN . Syntheses, crystal structures, and quantum chemistry calculation of two Ni(Ⅱ) coordination polymers. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 2031-2039. doi: 10.11862/CJIC.20240109
12. [12]
  Yadan SUN , Xinfeng LI , Qiang LIU , Oshio Hiroki , Yinshan MENG . Structures and magnetism of dinuclear Co complexes based on imine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2212-2220. doi: 10.11862/CJIC.20240131
13. [13]
  Yuanpeng Ye , Longfei Yao , Guofeng Liu . Engineering circularly polarized luminescence through symmetry manipulation in achiral tetraphenylpyrazine structures. Chinese Journal of Structural Chemistry, 2025, 44(2): 100460-100460. doi: 10.1016/j.cjsc.2024.100460
14. [14]
  Xiumei LI , Linlin LI , Bo LIU , Yaru PAN . Syntheses, crystal structures, and characterizations of two cadmium(Ⅱ) coordination polymers. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 613-623. doi: 10.11862/CJIC.20240273
15. [15]
  Chen Chen , Jinzhou Zheng , Chaoqin Chu , Qinkun Xiao , Chaozheng He , Xi Fu . An effective method for generating crystal structures based on the variational autoencoder and the diffusion model. Chinese Chemical Letters, 2025, 36(4): 109739-. doi: 10.1016/j.cclet.2024.109739
16. [16]
  Qihan Lin , Jiabin Xing , Yue-Yang Liu , Gang Wu , Shi-Jia Liu , Hui Wang , Wei Zhou , Zhan-Ting Li , Dan-Wei Zhang . taBOX: A water-soluble tetraanionic rectangular molecular container for conjugated molecules and taste masking for berberine and palmatine. Chinese Chemical Letters, 2024, 35(5): 109119-. doi: 10.1016/j.cclet.2023.109119
17. [17]
  Yuanzhe Lu , Yuanqin Zhu , Linfeng Zhong , Dingshan Yu . Long-lifespan aqueous alkaline and acidic batteries enabled by redox conjugated covalent organic polymer anodes. Chinese Journal of Structural Chemistry, 2024, 43(3): 100249-100249. doi: 10.1016/j.cjsc.2024.100249
18. [18]
  Xin-Tong Zhao , Jin-Zhi Guo , Wen-Liang Li , Jing-Ping Zhang , Xing-Long Wu . Two-dimensional conjugated coordination polymer monolayer as anode material for lithium-ion batteries: A DFT study. Chinese Chemical Letters, 2024, 35(6): 108715-. doi: 10.1016/j.cclet.2023.108715
19. [19]
  Yi Liu , Peng Lei , Yang Feng , Shiwei Fu , Xiaoqing Liu , Siqi Zhang , Bin Tu , Chen Chen , Yifan Li , Lei Wang , Qing-Dao Zeng . Topologically engineering of π-conjugated macrocycles: Tunable emission and photochemical reaction toward multi-cyclic polymers. Chinese Chemical Letters, 2024, 35(10): 109571-. doi: 10.1016/j.cclet.2024.109571
20. [20]
  Jinwei Zhang , Lipiao Bao , Xing Lu . Synthesis methodologies of conductive 2D conjugated metal-organic frameworks. Chinese Journal of Structural Chemistry, 2025, 44(4): 100459-100459. doi: 10.1016/j.cjsc.2024.100459

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(1006)
HTML views(25)

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