Citation: Zhang Jing, Wang Lina, Chen Xiaofei, Wang Yufeng, Niu Chengyan, Wu Lixin, Tang Zhiyong. Redox-Regulated Dynamic Self-Assembly of a Lindqvist-Type Polyoxometalate Complex[J]. Acta Physico-Chimica Sinica, ;2020, 36(9): 191200. doi: 10.3866/PKU.WHXB201912002 shu

Redox-Regulated Dynamic Self-Assembly of a Lindqvist-Type Polyoxometalate Complex

Zhang Jing ^1,2,, ,
Wang Lina ^1,3 ,
Chen Xiaofei ⁴ ,
Wang Yufeng ¹ ,
Niu Chengyan ¹ ,
Wu Lixin ⁴ ,
Tang Zhiyong ^2,,

1.
Institute of Applied Chemistry, Shanxi University, Taiyuan 030006, P. R. China
2.
CAS Key Laboratory of Nanosystem and Hierarchy Fabrication, National Center for Nanoscience and Technology, Beijing 100190, P. R. China
3.
College of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, P. R. China
4.
State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012, P. R. China

Corresponding author: Zhang Jing, jingzhang@sxu.edu.cn Tang Zhiyong, zytang@nanoctr.cn
Received Date: 2 December 2019
Revised Date: 20 December 2019
Accepted Date: 25 December 2019
Available Online: 3 January 2020
Fund Project: the National Natural Science Foundation of China 21972081the National Natural Science Foundation of China 21502107The project was supported by the National Key Basic Research Program of China (2016YFA0200700), the National Natural Science Foundation of China (21972081, 21890381, 21721002, 21502107), the Frontier Science Key Project of Chinese Academy of Sciences (QYZDJ-SSW-SLH038), and the K. C. Wong Education Foundationthe Frontier Science Key Project of Chinese Academy of Sciences QYZDJSSW-SLH038the National Natural Science Foundation of China 21721002the National Key Basic Research Program of China 2016YFA0200700the National Natural Science Foundation of China 21890381

Dynamic regulation of self-assembly is of vital importance in chemistry, biology and material science thanks to its great potential for development of smart materials and devices. Polyoxometalates (POMs) are a class of functional inorganic nanoclusters, which has become one of the excellent building blocks for supramolecular self-assemblies, especially when covalently or non-covalently modified by organic species. As typical stimuli-responsive functional clusters, the POMs could be photochemically or electrochemically reduced to mixed-valence states, of which the structural integrity remains even after encountering stepwise multi-electron redox process. The intriguing photochromism of the POMs in different states exhibits distinct photophysical properties, which motivates us to exploit the dynamic self-assemblies of POM-based complexes. The divalent Lindqvist-type hexamolybdate cluster [Mo₆O₁₉]^2- is one of the least negative-charged POMs, which is the ideal building blocks to construct novel assembly structures. Based on this motivation, herein, a single chain surfactant-encapsulated polyoxometalate (POM) complex (ODTA)₂[Mo₆O₁₉] was prepared by simple counterion replacement of Lindqvist-type (TBA)₂[Mo₆O₁₉] with octadecyltrimethylammonium (ODTA) in acetonitrile solution. The structure of the POM complex was confirmed by ¹H nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and elemental analysis. The solution of complex (ODTA)₂[Mo₆O₁₉] in the mixed solvents of acetonitrile and isopropanol with the volume ration of 4 to 1 exhibited reversible photochromism upon alternate UV light irradiation and air exposure. Upon UV light irradiation, the light yellow transparent solution of (ODTA)₂[Mo₆O₁₉] turned into blue quickly. The new broad absorption band appearing at ca.751 nm assigned to the Mo^V → Mo^VI intervalence charge-transfer (IVCT) transition, indicated the formation of reduced POM, as revealed by UV-Vis absorption spectra. After exposed to air, the blue solution was bleached. The alternate photochromism could be conducted for multiple cycles. Helical self-assembled morphology of (ODTA)₂[Mo₆O₁₉] was formed in acetonitrile/isopropanol, characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) methods. More interestingly, morphology transformation of the complex from helical strips to spherical assemblies occurred accompanied by photochromism occurrence. The morphology evolution during the photochromism process experienced from shortened helical strips through sea urchin-like aggregates to spherical assemblies. Most significantly, the helical assemblies could be recovered again after air oxidation, implying the reversible morphology transformation driven by redox stimulus. The redox-modulated reversible self-assembly is driven by the variation of electrostatic attraction between organic cations and inorganic anions as well as the electrostatic repulsion between inorganic ionic clusters, proved by X-ray photoelectron spectroscopy (XPS) and ¹H NMR spectra. The results will contribute to better understanding the mechanism of dynamic assemblies and inspire the precise fabrication of advanced smart materials.
- Polyoxometalate,
- Morphology control,
- Redox,
- Photochromism,
- Dynamic self-assembly
1. [1]
  Chang, Y. C.; Jiao, Y.; Symons, H. E.; Xu, J. F.; Faul, C. F. J.; Zhang, X. Chem. Soc. Rev. 2019, 48, 989. doi: 10.1039/C8CS00806J doi: 10.1039/C8CS00806J
2. [2]
  Jin, H. J.; Li, H. P.; Zhu, Z. Y.; Huang, J. B.; Xiao, Y. L.; Yan, Y. Angew. Chem. Int. Ed. 2019, doi: 10.1002/anie.201911845 doi: 10.1002/anie.201911845
3. [3]
  Ji, X. F.; Chen, W.; Long, L. L.; Huang, F. H.; Sessler, J. L. Chem. Sci. 2018, 9, 7746. doi: 10.1039/c8sc03463j doi: 10.1039/c8sc03463j
4. [4]
  Song, Y. F.; Tsunashima, R. Chem. Soc. Rev. 2012, 41, 7384. doi: 10.1039/c2cs35143a doi: 10.1039/c2cs35143a
5. [5]
  Liu, H. K.; Ren, L. J.; Wu, H.; Ma, Y. L.; Richter, S.; Godehardt, M.; Kubel, C.; Wang, W. J. Am. Chem. Soc. 2019, 141, 831. doi: 10.1021/jacs8b08016 doi: 10.1021/jacs8b08016
6. [6]
  Xia, C. X.; Wang, Z.; Sun, D.; Jiang, B. L.; Xin, X. Langmuir 2017, 33, 13242. doi: 10.1021/acs.langmuir.7b03495 doi: 10.1021/acs.langmuir.7b03495
7. [7]
  He, P. L.; Xu, B.; Xu, X. B.; Song, L.; Wang, X.; Chem. Sci. 2016, 7, 1011. doi: 10.1 039/c5sc03554f doi: 10.1039/c5sc03554f
8. [8]
  Wang, S. S.; Yang, G. Y. Chem. Rev. 2015, 115, 4893. doi: 10.1021/cr500390v doi: 10.1021/cr500390v
9. [9]
  Shi, N.; Wang, R.; Wang, X.; Tan, J.; Guan, Y.; Li, Z.; Wan, X.; Zhang, J. Chem. Commun. 2019, 55, 1136. doi: 10.1039/c8cc09154d doi: 10.1039/c8cc09154d
10. [10]
  Zhang, G. P.; Zhu, H. X.; Chen, M. J.; Li, H. G.; Yuan, Y.; Ma, T. T.; Hao, J. C. Chem. Eur. J. 2017, 23, 7278. doi: 10.1002/chem.201605651 doi: 10.1002/chem.201605651
11. [11]
  Wang, Y. C.; Li, F. Y.; Xu, L.; Jiang, N.; Liu, X. Z. Dalton Trans. 2013, 42, 5839. doi: 10.1039/C3DT32658F doi: 10.1039/C3DT32658F
12. [12]
  Sun, Z. X.; Li, F. Y.; Zhao, M. L.; Xu, L.; Fang, S. N. Electrochem. Commun. 2013, 30, 38. doi: 10.1016/j.elecom.2013.02.006 doi: 10.1016/j.elecom.2013.02.006
13. [13]
  Zhao, J.; Li, K. X.; Wan, K. W.; Sun, T. D.; Zheng, N. N.; Zhu, F. J.; Ma, J. C.; Jiao, J.; Li, T. C.; Ni, J.; et al. Angew. Chem. Int. Ed. 2019, 58, 2. doi: 10.1002/anie.201910521 doi: 10.1002/anie.201910521
14. [14]
  Zhang, Y.; Wu, L. L.; Zhao, X. Y.; Zhao, Y. N.; Tan, H. Q.; Zhao, X.; Ma, Y. Y.; Zhao, Z.; Song, S. Y.; Wang, Y. H.; et al. Adv. Energy Mater. 2018, 8, 1801139. doi: 10.1002/aenm.201801139 doi: 10.1002/aenm.201801139
15. [15]
  Yan, Y.; Wang, H. B.; Li, B.; Hou, G. F.; Yin, Z. D.; Wu, L. X.; Yam, V. W. W. Angew. Chem. Int. Ed. 2010, 48, 9233. doi: 10.1002/anie.201004143 doi: 10.1002/anie.201004143
16. [16]
  Yu, S. J.; Han, Y. K.; Wang, W. Polymer 2019, 162, 73. doi: 10.1016/j.polymer.2018.12.035 doi: 10.1016/j.polymer.2018.12.035
17. [17]
  Li, H.; Jia, Y.; Wang, A. H.; Cui, W.; Ma, H. C.; Feng, X. Y.; Li. J. B. Chem. Eur. J. 2014, 20, 499. doi: 10.1002/chem.201302660 doi: 10.1002/chem.201302660
18. [18]
  Yan, J.; Zheng, X. W.; Yao, J. H.; Xu, P.; Miao, Z. L.; Li, J. L.; Lv Z. D.; Zhang, Q. Y.; Yan, Y. J. Organomet. Chem. 2019, 884, 1. doi: 10.1016/j.jorganchem.2019.01.012 doi: 10.1016/j.jorganchem.2019.01.012
19. [19]
  Li, B.; Li, W.; Li, H. L.; Wu, L. X. Acc. Chem. Res. 2017, 50, 1391. doi: 10.1021/acs.accounts.7b00055 doi: 10.1021/acs.accounts.7b00055
20. [20]
  Yin, P. C.; Li, D.; Liu, T. B. Chem. Soc. Rev. 2012, 41, 7368. doi: 10.1039/c2cs35176e doi: 10.1039/c2cs35176e
21. [21]
  Nisar, A.; Zhuang, J.; Wang, X. Adv. Mater. 2011, 23, 1130. doi: 10.1002/adma.201003520 doi: 10.1002/adma.201003520
22. [22]
  Gao, Q.; Li, F. Y.; Wang, Y. C.; Xu, L.; Bai, J.; Wang, Y. Dalton Trans. 2014, 43, 941. doi: 10.1039/c3dt52882k doi: 10.1039/c3dt52882k
23. [23]
  Polarz, S.; Odendal, J, A.; Hermann, S.; Klaiber, A. Current Opinion Colloid Interface Sci. 2015, 20, 151. doi: 10.1016/j.cocis.2015.07.006 doi: 10.1016/j.cocis.2015.07.006
24. [24]
  Yang, Y.; Wang, Y. Z.; Li, H. L.; Li, W.; Wu, L. X. Chem. Eur. J. 2010, 16, 8062. doi: 10.1002/chem.201000198 doi: 10.1002/chem.201000198
25. [25]
  Zhang, J.; Chen, X.; Li, W.; Li, B.; Wu, L. Langmuir 2017, 33, 12750. doi: 10.1021/acs.langmuir.7b01259 doi: 10.1021/acs.langmuir.7b01259
26. [26]
  Yan, X. H.; Zhu, P. L.; Fei, J. B.; Li, J. B. Adv. Mater. 2010, 22, 1283. doi: 10.1002/adma.200901889 doi: 10.1002/adma.200901889
27. [27]
  Wang, R.; Cui, J.; Wan, X.; Zhang, J. Chem. Commun. 2019, 55, 4949. doi: 10.1039/c9cc01015g doi: 10.1039/c9cc01015g
28. [28]
  Sun, N.; Wu, A. L.; Yu, Y.; Gao, X. P.; Zheng, L. Q. Chem. Eur. J. 2019, 25, 6203. doi: 10.1002/chem.201900478 doi: 10.1002/chem.201900478
29. [29]
  Gu, H. X.; Bi, L. H.; Fu, Y.; Wang, N.; Liu, S. Q.; Tang, Z. Y. Chem. Sci. 2013, 4, 4371. doi: 10.1039/C3SC51778K doi: 10.1039/C3SC51778K
30. [30]
  Wang, Z. L.; Ma, Y.; Zhang, R. L.; Peng, A. D.; Liao, Q.; Cao, Z. W.; Fu, H. B.; Yao, J. N. Adv. Mater. 2009, 21, 1737. doi: 10.1002/adma.200803321 doi: 10.1002/adma.200803321
31. [31]
  Xiao, F. P.; Hao, J.; Zhang, J.; Lv, C. L.; Yin, P. C. Wang, L. S.; Wei, Y. G. J. Am. Chem. Soc. 2010, 132, 5956. doi: 10.1021/ja101671q doi: 10.1021/ja101671q
32. [32]
  Cao, X.; Zhang, L. Y.; Xu, T. Y.; Zhang, S. L.; Zhang, H.; Li, H. L.; Wu, L. X. Polym. Chem. 2016, 7, 3216. doi: 10.1039/c6py00514d doi: 10.1039/c6py00514d
33. [33]
  Zhang, J.; Hao, J.; Wei, Y. G.; Xiao, F. P.; Yin, P. C.; Wang, L. S. J. Am. Chem. Soc. 2010, 132, 14. doi: 10.1021/ja907535g doi: 10.1021/ja907535g
34. [34]
  Che, M.; Fournier, M.; Launay, J. J. Chem. Phys. 1979, 71, 1954. doi: 10.1063/1.438549 doi: 10.1063/1.438549
35. [35]
  Poulos, A. S.; Constantin, D.; Davidson. P.; Impéror, M.; Pansu, B.; Panine, P.; Nicole, L.; Sanchez, C. Langmuir 2008, 24, 6285. doi: 10.1021/la8004322 doi: 10.1021/la8004322
36. [36]
  Yin, P. C.; Wu, P. F.; Xiao, Z. C.; Li, D.; Bitterlich, E.; Zhang, J.; Cheng, P.; Vezenov, D. V.; Liu, T. B.; Wei, Y. G. Angew. Chem. Int. Ed. 2011, 50, 2521. doi: 10.1002/anie.201006144 doi: 10.1002/anie.201006144
37. [37]
  Zhang, H.; Wang, D. Y. Angew. Chem. Int. Ed. 2008, 47, 3984. doi: 10.1002/anie.200705537 doi: 10.1002/anie.200705537
38. [38]
  Zhang, J.; Li, W.; Wu, C.; Li, B.; Zhang, J.; Wu, L. X. Chem. Eur. J. 2013, 19, 8129. doi: 10.1002/chem.201300309 doi: 10.1002/chem.201300309
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