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A New Scheme to Prepare Polyoxovanadate-Polymer Hybrid Materials

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Abstract

Polyoxovanadates (POVs) have aroused increasing attentions in recent years because of their excellent catalytic properties and unique biochemical activities. The rational design and materialization of POVs towards practical applications remain a challenge. One main strategy for the preparation of polyoxometalate-based materials is to incorporate the inorganic metal-oxo clusters into organic polymers. However, there is rare report about POV-based polymer mainly because that the vanadium with high valence state in clusters have negative impact on the design and synthesis. In this communication, we provided a new scheme to prepare POV-based polymers by stepwise functionalization and free radical polymerization for the first time. The influence from different organic ligands to the polymerization was also discussed. The results indicate that the free radical polymerization in the POV-based inorganic–organic system has the same tendency as the pure organic system, providing a new vision for the rational design of advanced POV-based polymer materials.

Graphic Abstract

For the first time, polyoxovanadate clusters were successfully linked to organic polymers by free radical polymerization reaction, providing a new vision for the rational design of advanced polyoxovanadate-based hybrid materials.

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References

  1. Monakhov KY, Bensch W, Kogerler P (2015). Semimetal-functionalised polyoxovanadates. Chem. Soc. Rev.44 (23): 8443−8483. https://doi.org/10.1039/c5cs00531k

    Article  PubMed  CAS  Google Scholar 

  2. Anyushin AV, Kondinski A, Parac-Vogt TN (2020). Hybrid polyoxometalates as post-functionalization platforms: from fundamentals to emerging applications. Chem. Soc. Rev.49 (2): 382−432. https://doi.org/10.1039/c8cs00854j

    Article  PubMed  CAS  Google Scholar 

  3. Li J-K, Dong J, Wei C-P, Yang S, Chi Y-N, Xu Y-Q, Hu C-W (2017). Controllable synthesis of Lindqvist alkoxopolyoxovanadate clusters as heterogeneous catalysts for sulfoxidation of sulfides. Inorg. Chem.56 (10): 5748−5756. https://doi.org/10.1021/acs.inorgchem.7b00366

    Article  PubMed  CAS  Google Scholar 

  4. Zhang H-M, Yang J, Kan W-Q, Liu Y-Y, Ma J-F (2016). Photocatalytic properties and luminescent sensing for Cr3+ cations of polyoxovanadates-based inorganic–organic hybrid compounds with multiple Lewis basic sites. Cry. Grow. & Des.16 (1): 265−276. https://doi.org/10.1021/acs.cgd.5b01226

    Article  CAS  Google Scholar 

  5. Huang B, Ke D, Xiong Z, Wang Y, Hu K, Jiang P, Liang M, Xiao Z, Wu P (2020). Covalent hybrid materials between polyoxometalates and organic molecules for enhanced electrochemical properties. J. Mater. Sci.55 (13): 5554−5570. https://doi.org/10.1007/s10853-020-04404-0

    Article  CAS  Google Scholar 

  6. Hu X, Wang H, Huang B, Li N, Hu K, Wu B, Xiao Z, Wei Y, Wu P (2019). A new scheme for rational design and synthesis of polyoxovanadate hybrids with high antitumor activities. J. Inorg. Biochem.193: 130−132. https://doi.org/10.1016/j.jinorgbio.2019.01.013

    Article  PubMed  CAS  Google Scholar 

  7. Sullivan KP, Neiwert WA, Zeng H, Mehta AK, Yin Q, Hillesheim DA, Vivek S, Yin P, Collins-Wildman DL, Weeks ER, Liu T, Hill CL (2017). Polyoxometalate-based gelating networks for entrapment and catalytic decontamination. Chem. Commun.53 (83): 11480−11483. https://doi.org/10.1039/c7cc05657e

    Article  CAS  Google Scholar 

  8. Chen K, Bayaguud A, Li H, Chu Y, Zhang H, Jia H, Zhang B, Xiao Z, Wu P, Liu T, Wei Y (2018). Improved peroxidase-mimic property: Sustainable, high-efficiency interfacial catalysis with H2O2 on the surface of vesicles of hexavanadate-organic hybrid surfactants. Nano Res.11 (3): 1313−1321. https://doi.org/10.1007/s12274-017-1746-5

    Article  CAS  Google Scholar 

  9. Qi W, Wu L (2009). Polyoxometalate/polymer hybrid materials: fabrication and properties. Polym. Int.58 (11): 1217−1225. https://doi.org/10.1002/pi.2654

    Article  CAS  Google Scholar 

  10. Kalyani V, Satyanarayana V, Singh V, Pradeep C., Ghosh S, Sharma, S, Gonsalves K (2014). New polyoxometalates containing hybrid polymers and their potential for nano-patterning. Chem. Eur. J.21 (5): 2250−2258. https://doi.org/ 10.1002/chem.201405369

    Article  PubMed  CAS  Google Scholar 

  11. Kalyani V, Satyanarayana V, Sarkar A, Kumar A, Pal S, Ghosh S, Gonsalves K, Pradeep C (2015). A radiation sensitive hybrid polymer based on an Mn-Anderson polyoxometalate cluster and a UV active organic monomer: synergistic effects lead to improved photocurrent in a photoresponse device. RSC Adv.5 (46), 36727−36731. https://doi.org/ 10.1039/C5RA05550D

    Article  CAS  Google Scholar 

  12. Yan J, Huang HY, Miao ZL, Zhang QY, Yan Y (2019). Polyoxometalate-based hybrid supramolecular polymer via orthogonal metal coordination and reversible photo-cross-linking. Macromolecules52 (24): 9545−9554. https://doi.org/10.1021/acs.macromol.9b01825

    Article  CAS  Google Scholar 

  13. Li HL, Wu LX (2019). A perspective on polyoxometalates as versatile synthons for precisely hybridized polymer materials. Polym. Int.. https://doi.org/10.1002/pi.5948

    Article  Google Scholar 

  14. Zhai L, Li HL (2019). Polyoxometalate-polymer hybrid materials as proton exchange membranes for fuel cell applications. Molecules24 (19). 3425−3444 https://doi.org/10.3390/molecules24193425

    Article  PubMed Central  CAS  Google Scholar 

  15. Xu L, Lu M, Xu B, Wei Y, Peng Z, Powell DR (2002). Towards main-chain-polyoxometalate-containing hybrid polymers: a highly efficient approach to bifunctionalized organoimido derivatives of hexamolybdates. Angew. Chem. Int. Ed.41 (21): 4129−4132. https://doi.org/10.1002/1521-3773(20021104)41:21

    Article  CAS  Google Scholar 

  16. Moore AR, Kwen H, Beatty AM, Maatta EA (2000). Organoimido-polyoxometalates as polymer pendants. Chem. Commun.18: 1793−1794. https://doi.org/10.1039/B005022I

    Article  Google Scholar 

  17. Hu M-B, Hou Z-Y, Hao W-Q, Xiao Y, Yu W, Ma C, Ren L-J, Zheng P, Wang W (2013). POM–Organic–POSS cocluster: creating a dumbbell-shaped hybrid molecule for programming hierarchical supramolecular nanostructures. Langmuir29 (19): 5714−5722. https://doi.org/10.1021/la400802p

    Article  PubMed  CAS  Google Scholar 

  18. Zhang J, Huang Y, Li G, Wei Y (2019). Recent advances in alkoxylation chemistry of polyoxometalates: From synthetic strategies, structural overviews to functional applications. Coordin. Chem. Rev. 378: 395−414. https://doi.org/https://doi.org/10.1016/j.ccr.2017.10.025

    Article  CAS  Google Scholar 

  19. Huang B, Wang N, Yang K, Ke D, Fang Y, Hu X, Wu B, Xiao Z, Wu P, Wei Y (2018). Stepwise syntheses and supramolecular assemblies of a series of polyoxovanadate hybrids with various architectures. New J. Chem.42 (8): 5853−5858. https://doi.org/10.1039/c7nj04727d

    Article  CAS  Google Scholar 

  20. Xu X, Spasojevic-de Bire A, Ghermani NE, Wei Y, Novakovic S, Bosnjakovic-Pavlovic N, Wu P (2017). Experimental evidence of charge transfer in a functionalized hexavanadate: a high resolution X-ray diffraction study. Phys. Chem. Chem. Phys.19 (28): 18162−18166. https://doi.org/10.1039/C7CP01840A

    Article  PubMed  CAS  Google Scholar 

  21. Xiao Z, Chen K, Wu B, Li W, Wu P, Wei Y (2016). An easy way to construct polyoxovanadate-based organic−inorganic hybrids by stepwise functionalization. Eur. J. Inorg. Chem.6: 808−811. https://doi.org/10.1002/ejic.201501297

    Article  CAS  Google Scholar 

  22. Huang B, Xiao Z, Wu B, Hu X, Hu X, Wu P, Wei Y (2017). Synthesis, crystal structure and spectroscopic studies of a series of hexavanadate hybrids with multiple functional groups. Inorg. Chem. Front.4 (1): 165−170. https://doi.org/10.1039/c6qi00302h

    Article  CAS  Google Scholar 

  23. Hu M-B, Xia N, Yu W, Ma C, Tang J, Hou Z-Y, Zheng P, Wang W (2012). A click chemistry approach to the efficient synthesis of polyoxometalate–polymer hybrids with well-defined structures. Polym. Chem.3 (3): 617−620. https://doi.org/10.1039/C2PY00546H

    Article  CAS  Google Scholar 

  24. Han Y, Xiao Y, Zhang Z, Liu B, Zheng P, He S, Wang W (2009). Synthesis of polyoxometalate−polymer hybrid polymers and their hybrid vesicular assembly. Macromolecules42 (17): 6543−6548. https://doi.org/10.1021/ma9011686

    Article  CAS  Google Scholar 

  25. Yu S-J, Han Y-K, Wang W (2019). Unravelling concentration-regulated self-assembly of a protonated polyoxometalate-polystyrene hybrid. Polymer162: 73−79. https://doi.org/https://doi.org/10.1016/j.polymer.2018.12.035

    Article  CAS  Google Scholar 

  26. Tang J, Li X-Y, Wu H, Ren L-J, Zhang Y-Q, Yao H-X, Hu M-B, Wang W (2016). Tube-graft-Sheet nano-objects created by a stepwise self-assembly of polymer-polyoxometalate hybrids. Langmuir32 (2): 460−467. https://doi.org/10.1021/acs.langmuir.5b04504

    Article  PubMed  CAS  Google Scholar 

  27. Zhu Y, Huang Y, Li Q, Zang D, Gu J, Tang Y, Wei Y (2020). Polyoxometalate-based photoactive hybrid: uncover the first crystal structure of covalently linked hexavanadate-porphyrin molecule. Inorg. Chem.59 (4): 2575–2583. https://doi.org/ 10.1021/acs.inorgchem.9b03540

    Article  PubMed  CAS  Google Scholar 

  28. Gu Y, Li Q, Huang Y, Zhu Y, Wei Y, Ruhlmann L (2020) Polyoxovanadate-iodobodipy supramolecular assemblies: new agents for high efficiency cancer photochemotherapy. Chem. Commun.56 (19): 2869–2872. https://doi.org/ 10.1039/C9CC09944A

    Article  CAS  Google Scholar 

  29. Jia H, Li Q, Bayaguud A, Huang Y, She S, Chen K, Wei Y (2018) Diversified polyoxovanadate derivatives obtained by copper(i)-catalysed azide–alkyne cycloaddition reaction: their synthesis and structural characterization. Dalton Trans.47 (2): 577–584. https://doi.org/ 10.1039/C7DT03822D

    Article  PubMed  CAS  Google Scholar 

  30. Bayaguud A, Li J, She S, Wei Y (2017) A simple synthetic route to polyoxovanadate-based organic–inorganic hybrids using EEDQ as an ester coupling agent. Dalton Trans. 46 (14): 4602–4608. https://doi.org/ 10.1039/C7DT00274B

    Article  PubMed  CAS  Google Scholar 

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Acknowledgements

Bo Huang appreciate the kind helps from Hailin Wu (Zhejiang University). This work is supported by National Natural Science Foundation of China (No. 21271068, 21401050), the Natural Science Foundation of Hubei Province (No. 2015CFA131) and Wuhan Applied Basic Research Program (No. 2014010101010020).

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Authors and Affiliations

  1. Institute of POM-Based Materials, Hubei Provincial Key Laboratory of Green Materials for Light Industry, Hubei University of Technology, Wuhan, 430068, China

    Bo Huang, Zicheng Xiao & Pingfan Wu

  2. CAS Center for Excellence in Nanoscience, CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing, 100190, China

    Bo Huang

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  1. Bo Huang
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  2. Zicheng Xiao
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Correspondence to Zicheng Xiao or Pingfan Wu.

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Huang, B., Xiao, Z. & Wu, P. A New Scheme to Prepare Polyoxovanadate-Polymer Hybrid Materials. J Clust Sci 32, 1739–1745 (2021). https://doi.org/10.1007/s10876-020-01907-3

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