Skip to main content
SpringerLink
Log in

Difluoroborate-based conjugated organic polymer: a high-performance heterogeneous photocatalyst for oxidative coupling reactions

  • Chemical routes to materials
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

A photoactive difluoroborate-based conjugated organic polymer (B-COP) with A3B2-type donor–acceptor arrays in the polymer framework was synthesized by direct polycondensation and exhibited amorphous structure, high thermal and photophysical stability. The B-COP was shown to be a highly efficient heterogeneous photocatalyst for a wide range of photocatalytic transformations, including the oxidative coupling of primary amine and cross-dehydrogenative coupling reactions between tetrahydroisoquinolines and nucleophiles such as nitromethane, nitroethane, acetone and phenylethyl ketone.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Figure 1

Similar content being viewed by others

References

  1. Sun CL, Li BJ, Shi ZJ (2011) Direct C–H transformation via iron catalysis. Chem Rev 111:1293–1314

    Article  CAS  Google Scholar 

  2. Godula K, Sames D (2006) C–H bond functionalization in complex organic synthesis. Science 312:67–72

    Article  CAS  Google Scholar 

  3. Bergman RG (2007) Organometallic chemistry: C–H activation. Nature 446:391–393

    Article  CAS  Google Scholar 

  4. Li CJ (2009) Cross-dehydrogenative coupling (CDC): exploring C–C bond formations beyond functional group transformations. Acc Chem Res 42:335–344

    Article  CAS  Google Scholar 

  5. Li Z, Li CJ (2005) Highly efficient copper-catalyzed nitro-mannich type reaction: cross-dehydrogenative-coupling between sp3 C–H bond and sp3 C–H bond. J Am Chem Soc 127:3672–3673

    Article  CAS  Google Scholar 

  6. Condie AG, González-Gómez JC, Stephenson CRJ (2010) Visible-light photoredox catalysis: aza-henry reactions via C–H functionalization. J Am Chem Soc 132:1464–1465

    Article  CAS  Google Scholar 

  7. Wu CJ, Zhong JJ, Meng QY, Lei T, Gao XW, Tung CH, Wu LZ (2015) Cobalt-catalyzed cross-dehydrogenative coupling reaction in water by visible light. Org Lett 17:884–887

    Article  CAS  Google Scholar 

  8. Wang B, Shelar DP, Han XZ, Li TT, Guan X, Lu W, Liu K, Chen Y, Fu WF, Che CM (2015) Long-lived excited states of zwitterionic copper(I) complexes for photoinduced cross-dehydrogenative coupling reactions. Chem Eur J 21:1184–1190

    Article  CAS  Google Scholar 

  9. Zhong J, Meng Q, Wang G, Liu Q, Chen B, Feng K, Tung C, Wu L (2013) A highly efficient and selective aerobic cross-dehydrogenative-coupling reaction photocatalyzed by a platinum(II) terpyridyl complex. Chem Eur J 19:6443–6450

    Article  CAS  Google Scholar 

  10. Neumann M, Zeitler K (2012) Application of microflow conditions to visible light photoredox catalysis. Org Lett 14:2658–2661

    Article  CAS  Google Scholar 

  11. Tucker JW, Zhang Y, Jamison TF, Stephenson CRJ (2012) Visible-light photoredox catalysis in flow. Angew Chem Int Ed 51:4144–4147

    Article  CAS  Google Scholar 

  12. Gandy MN, Raston CL, Stubbs KA (2015) Photoredox catalysis under shear using thin film vortex microfluidics. Chem Commun 51:11041–11044

    Article  CAS  Google Scholar 

  13. Möhlmann L, Baar M, Rieß J, Antonietti M, Wang X, Blechert S (2012) Carbon nitride-catalyzed photoredox C–C bond formation with N-aryltetrahydroisoquinolines. Adv Synth Catal 354:1909–1913

    Article  Google Scholar 

  14. Mitkina T, Stanglmair C, Setzer W, Gruber M, Kisch H, König B (2012) Visible light mediated homo- and heterocoupling of benzyl alcohols and benzyl amines on polycrystalline cadmium sulfide. Org Biomol Chem 10:3556–3561

    Article  CAS  Google Scholar 

  15. Rueping M, Zoller J, Fabry DC, Poscharny K, Koenigs RM, Weirich TE, Mayer J (2012) Light-mediated heterogeneous cross dehydrogenative coupling reactions: metal oxides as efficient, recyclable, photoredox catalysts in C–C bond forming reactions. Chem Eur J 18:3478–3481

    Article  CAS  Google Scholar 

  16. Wang C, Xie Z, DeKrafft KE, Lin W (2011) Doping metal-organic frameworks for water oxidation, carbon dioxide reduction, and organic photocatalysis. J Am Chem Soc 133:13445–13454

    Article  CAS  Google Scholar 

  17. Xie Z, Wang C, DeKrafft KE, Lin W (2011) Highly stable and porous cross-linked polymers for efficient photocatalysis. J Am Chem Soc 133:2056–2059

    Article  CAS  Google Scholar 

  18. Windle CD, Perutz RN (2012) Advances in molecular photocatalytic and electrocatalytic CO2 reduction. Coord Chem Rev 256:2562–2570

    Article  CAS  Google Scholar 

  19. Liu W, Su Q, Ju P, Guo B, Zhou H, Li G, Wu Q (2017) A hydrazone-based covalent organic framework as an efficient and reusable photocatalyst for the cross-dehydrogenative coupling reaction of N-aryltetrahydroisoquinolines. Chemsuschem 10:664–669

    Article  CAS  Google Scholar 

  20. Ding S, Wang W (2013) Covalent organic frameworks (COFs): from design to applications. Chem Soc Rev 42:548–568

    Article  CAS  Google Scholar 

  21. Gu C, Huang N, Wu Y, Xu H, Jiang DL (2015) Design of highly photofunctional porous polymer films with controlled thickness and prominent microporosity. Angew Chem Int Ed 54:11540–11544

    Article  CAS  Google Scholar 

  22. Li D, Zhang H, Wang Y (2013) Four-coordinate organoboron compounds for organic light-emitting diodes (OLEDs). Chem Soc Rev 42:8416–8433

    Article  CAS  Google Scholar 

  23. Xu HS, Ding SY, An WK, Wu H, Wang W (2016) Constructing crystalline covalent organic frameworks from chiral building blocks. J Am Chem Soc 138:11489–11492

    Article  CAS  Google Scholar 

  24. Zhai L, Liu M, Xue P, Sun J, Gong P, Zhang Z, Sun J, Lu R (2016) Nanofibers generated from nonclassical organogelators based on difluoroboron β-diketonate complexes to detect aliphatic primary amine vapors. J Mater Chem C 4:7939–7947

    Article  CAS  Google Scholar 

  25. Zhuang X, Zhao W, Zhang F, Cao Y, Liu F, Bi S, Feng X (2016) A two-dimensional conjugated polymer framework with fully sp2-bonded carbon skeleton. Polym Chem 7:4176–4181

    Article  CAS  Google Scholar 

  26. Ding X, Guo J, Feng X, Honsho Y, Guo J, Seki S, Maitarad P, Saeki A, Nagase S, Jiang D (2011) Synthesis of metallophthalocyanine covalent organic frameworks that exhibit high carrier mobility and photoconductivity. Angew Chem Int Ed 50:1289–1293

    Article  CAS  Google Scholar 

  27. Bartling H, Eisenhofer A, König B, Gschwind RM (2016) The photocatalyzed Aza-Henry reaction of N-aryltetrahydroisoquinolines: comprehensive mechanism, H•- versus H+- abstraction and background reactions. J Am Chem Soc 138:11860–11871

    Article  CAS  Google Scholar 

  28. Liras M, Pintado-Sierra M, Iglesias M, Sánchez F (2016) A deprotection strategy of a BODIPY conjugated porous polymer to obtain a heterogeneous (dipyrrin)(bipyridine)ruthenium(II) visible light photocatalyst. J Mater Chem A 4:17274–17278

    Article  CAS  Google Scholar 

  29. Rueping M, Vila C, Koenigs RM, Poscharny K, Fabry DC (2011) Dual catalysis: combining photoredox and Lewis base catalysis for direct Mannich reactions. Chem Commun 47:2360–2362

    Article  CAS  Google Scholar 

  30. Liu Q, Li YN, Zhang HH, Chen B, Tung CH, Wu LZ (2012) Beactivity and mechanistic insight into visible-light-induced aerobic cross-dehydrogenative coupling reaction by organophotocatalysts. Chem Eur J 18:620–627

    Article  CAS  Google Scholar 

  31. Tibbetts JD, Carbery DR, Emanuelsson EAC (2017) An in-depth study of the use of Eosin Y for the solar photocatalytic oxidative coupling of benzylic amines. ACS Sustainable Chem Eng 5:9826–9835

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 51703076) and the Excellent Young Teachers Program of Jilin University. Q.S. thanks the open projects in State Key Lab of Inorganic Synthesis and Preparative Chemistry, Jilin University.

Author information

Authors and Affiliations

  1. College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun, 130012, People’s Republic of China

    Wanting Liu, Shujie Wu, Qing Su, Bixuan Guo, Pengyao Ju & Qiaolin Wu

  2. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, 2699 Qianjin Street, Changchun, 130012, People’s Republic of China

    Guanghua Li

Authors
  1. Wanting Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Shujie Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Qing Su
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Bixuan Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Pengyao Ju
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Guanghua Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Qiaolin Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Qing Su or Qiaolin Wu.

Ethics declarations

Conflicts of interest

All the authors declare that they have no conflicts of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 1651 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, W., Wu, S., Su, Q. et al. Difluoroborate-based conjugated organic polymer: a high-performance heterogeneous photocatalyst for oxidative coupling reactions. J Mater Sci 54, 1205–1212 (2019). https://doi.org/10.1007/s10853-018-2893-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-018-2893-0

Keywords

Search

Navigation