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Photoredox catalysis using infrared light via triplet fusion upconversion

Nature volume 565, pages 343–346 (2019)Cite this article

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An Author Correction to this article was published on 15 May 2019

This article has been updated

Abstract

Recent advances in photoredox catalysis have made it possible to achieve various challenging synthetic transformations, polymerizations and surface modifications1,2,3. All of these reactions require ultraviolet- or visible-light stimuli; however, the use of visible-light irradiation has intrinsic challenges. For example, the penetration of visible light through most reaction media is very low, leading to problems in large-scale reactions. Moreover, reactants can compete with photocatalysts for the absorption of incident light, limiting the scope of the reactions. These problems can be overcome by the use of near-infrared light, which has a much higher penetration depth through various media, notably biological tissue4. Here we demonstrate various photoredox transformations under infrared radiation by utilizing the photophysical process of triplet fusion upconversion, a mechanism by which two low-energy photons are converted into a higher-energy photon. We show that this is a general strategy applicable to a wide range of photoredox reactions. We tune the upconversion components to adjust the output light, accessing both orange light and blue light from low-energy infrared light, by pairwise manipulation of the sensitizer and annihilator. We further demonstrate that the annihilator itself can be used as a photocatalyst, thus simplifying the reaction. This approach enables catalysis of high-energy transformations through several opaque barriers using low-energy infrared light.

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Fig. 1: The NIR-to-orange and NIR-to-blue upconversion strategy.
Fig. 2: Selected examples of reactions driven by NIR light.
Fig. 3: Material penetration experiments.
Fig. 4: Application of the Beer–Lambert law to blue and NIR light.

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Data availability

The data that support the findings of this study are available from the corresponding authors on reasonable request.

Change history

  • 15 May 2019

    In Fig. 1c of this Letter, the orange axis label of the graph should have read ‘FDPP upconversion photoluminescence (AU)’ instead of ‘TTBP upconversion photoluminescence (AU)’. This has been corrected online.

References

  1. Prier, C. K., Rankic, D. A. & MacMillan, D. W. C. Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis. Chem. Rev. 113, 5322–5363 (2013).

    Article  CAS  Google Scholar 

  2. Romero, N. A. & Nicewicz, D. A. Organic photoredox catalysis. Chem. Rev. 116, 10075–10166 (2016).

    Article  CAS  Google Scholar 

  3. Cambié, D., Bottecchia, C., Straathof, N. J. W., Hessel, V. & Noël, T. Applications of continuous-flow photochemistry in organic synthesis, material science, and water treatment. Chem. Rev. 116, 10276–10341 (2016).

    Article  Google Scholar 

  4. Smith, A. M., Mancini, M. C. & Nie, S. Bioimaging: second window for in vivo imaging. Nat. Nanotechnol. 4, 710–711 (2009).

    Article  ADS  CAS  Google Scholar 

  5. Arias-Rotondo, D. M. & McCusker, J. K. The photophysics of photoredox catalysis: a roadmap for catalyst design. Chem. Soc. Rev. 45, 5803–5820 (2016).

    Article  CAS  Google Scholar 

  6. Le, C. C. et al. A general small-scale reactor to enable standardization and acceleration of photocatalytic reactions. ACS Cent. Sci. 3, 647–653 (2017).

    Article  CAS  Google Scholar 

  7. Zhou, J., Liu, Q., Feng, W., Sun, Y. & Li, F. Upconversion luminescent materials: advances and applications. Chem. Rev. 115, 395–465 (2015).

    Article  CAS  Google Scholar 

  8. Schulze, T. F. & Schmidt, T. W. Photochemical upconversion: present status and prospects for its application to solar energy conversion. Energy Environ. Sci. 8, 103–125 (2015).

    Article  CAS  Google Scholar 

  9. Park, Y. I., Lee, K. T., Suh, Y. D. & Hyeon, T. Upconverting nanoparticles: a versatile platform for wide-field two-photon microscopy and multi-modal in vivo imaging. Chem. Soc. Rev. 44, 1302–1317 (2015).

    Article  CAS  Google Scholar 

  10. Zhou, Y. et al. An upconverted photonic nonvolatile memory. Nat. Commun. 5, 4720 (2014).

    Article  CAS  Google Scholar 

  11. Viger, M. L., Grossman, M., Fomina, N. & Almutairi, A. Low power upconverted near-IR light for efficient polymeric nanoparticle degradation and cargo release. Adv. Mater. 25, 3733–3738 (2013).

    Article  CAS  Google Scholar 

  12. He, S. et al. Ultralow-intensity near-infrared light induces drug delivery by upconverting nanoparticles. Chem. Commun. 51, 431–434 (2015).

    Article  CAS  Google Scholar 

  13. Chen, Z., Sun, W., Butt, H.-J. & Wu, S. Upconverting-nanoparticle-assisted photochemistry induced by low-intensity near-infrared light: how low can we go? Chem. Eur. J. 21, 9165–9170 (2015).

    Article  CAS  Google Scholar 

  14. Askes, S. H. C., Bahreman, A. & Bonnet, S. Activation of a photodissociative ruthenium complex by triplet–triplet annihilation upconversion in liposomes. Angew. Chem. Int. Ed. 53, 1029–1033 (2014).

    Article  CAS  Google Scholar 

  15. Mahboub, M., Huang, Z. & Tang, M. L. Efficient infrared-to-visible upconversion with subsolar irradiance. Nano Lett. 16, 7169–7175 (2016).

    Article  ADS  CAS  Google Scholar 

  16. Majek, M., Faltermeier, U., Dick, B., Pérez-Ruiz, R. & Jacobi von Wangelin, A. Application of visible-to-UV photon upconversion to photoredox catalysis: the activation of aryl bromides. Chem. Eur. J. 21, 15496–15501 (2015).

    Article  CAS  Google Scholar 

  17. Häring, M., Pérez-Ruiz, R., Jacobi von Wangelin, A. & Díaz, D. D. Intragel photoreduction of aryl halides by green-to-blue upconversion under aerobic conditions. Chem. Commun. 51, 16848–16851 (2015).

    Article  Google Scholar 

  18. Singh-Rachford, T. N. & Castellano, F. N. Low power visible-to-UV upconversion. J. Phys. Chem. A 113, 5912–5917 (2009).

    Article  CAS  Google Scholar 

  19. Singh-Rachford, T. N. & Castellano, F. N. Photon upconversion based on sensitized triplet–triplet annihilation. Coord. Chem. Rev. 254, 2560–2573 (2010).

    Article  CAS  Google Scholar 

  20. Hartnett, P. E. et al. Effects of crystal morphology on singlet exciton fission in diketopyrrolopyrrole thin films. J. Phys. Chem. B 120, 1357–1366 (2016).

    Article  CAS  Google Scholar 

  21. Singh-Rachford, T. N. & Castellano, F. N. Pd(II) phthalocyanine-sensitized triplet–triplet annihilation from rubrene. J. Phys. Chem. A 112, 3550–3556 (2008).

    Article  CAS  Google Scholar 

  22. Neumann, M., Füldner, S., König, B. & Zeitler, K. Metal-free, cooperative asymmetric organophotoredox catalysis with visible light. Angew. Chem. Int. Ed. 50, 951–954 (2011).

    Article  CAS  Google Scholar 

  23. Mashraqui, S. H. & Kellogg, R. M. 3-Methyl-2,3-dihydrobenzothiazoles as reducing agent. Dye enhanced photoreactions. Tetrahedr. Lett. 26, 1453–1456 (1985).

    Article  CAS  Google Scholar 

  24. Natarajan, P., Kumar, N. & Sharma, M. Visible light-mediated intramolecular C–H arylation of diazonium salts of N-(2-aminoaryl)benzoimines: a facile synthesis of 6-arylphenanthridines. Org. Chem. Front. 3, 1265–1270 (2016).

    Article  CAS  Google Scholar 

  25. Sommer, J. R. et al. Photophysical properties of near-infrared phosphorescent π-extended platinum porphyrins. Chem. Mater. 23, 5296–5304 (2011).

    Article  CAS  Google Scholar 

  26. Deng, F., Sommer, J. R., Myahkostupov, M., Schanze, K. S. & Castellano, F. N. Near-IR phosphorescent metalloporphyrin as a photochemical upconversion sensitizer. Chem. Commun. 49, 7406–7408 (2013).

    Article  CAS  Google Scholar 

  27. Sasaki, Y., Amemori, S., Kouno, H., Yanai, N. & Kimizuka, N. Near infrared-to-blue photon upconversion by exploiting direct S–T absorption of a molecular sensitizer. J. Mater. Chem. C 5, 5063–5067 (2017).

    Article  CAS  Google Scholar 

  28. Ischay, M. A., Anzovino, M. E., Du, J. & Yoon, T. P. Efficient visible light photocatalysis of [2+2] enone cycloadditions. J. Am. Chem. Soc. 130, 12886–12887 (2008).

    Article  CAS  Google Scholar 

  29. Miyake, G. M. & Theriot, J. C. Perylene as an organic photocatalyst for the radical polymerization of functionalized vinyl monomers through oxidative quenching with alkyl bromides and visible light. Macromolecules 47, 8255–8261 (2014).

    Article  ADS  CAS  Google Scholar 

  30. Tucker, J. W., Zhang, Y., Jamison, T. F. & Stephenson, C. R. J. Visible-light photoredox catalysis in flow. Angew. Chem. Int. Ed. 51, 4144–4147 (2012).

    Article  CAS  Google Scholar 

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Acknowledgements

L.M.C. thanks the National Science Foundation (NSF CAREER DMR-1351293) for funding. A.B.P. thanks the NSF Graduate Research Fellowship Program (DGE-16-44869). D.N.C. is supported by the Rowland Fellowship at the Rowland Institute at Harvard. T.R. thanks the National Institute of General Medical Sciences (GM125206).

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Author notes

  1. These authors contributed equally: Benjamin D. Ravetz, Andrew B. Pun

Authors and Affiliations

  1. Department of Chemistry, Columbia University, New York, NY, USA

    Benjamin D. Ravetz, Andrew B. Pun, Emily M. Churchill, Tomislav Rovis & Luis M. Campos

  2. Rowland Institute at Harvard University, Cambridge, MA, USA

    Daniel N. Congreve

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Contributions

A.B.P. and D.N.C. carried out the upconversion experiments. B.D.R., A.B.P. and E.M.C. performed and analysed the photoredox and materials penetration experiments. D.N.C., T.R. and L.M.C. initiated and directed the study, and wrote the manuscript with contributions from all authors.

Corresponding authors

Correspondence to Daniel N. Congreve, Tomislav Rovis or Luis M. Campos.

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A provisional patent has been filed on this technology by the institutions on behalf of the authors of this work (US Provisional Application 62/641,739).

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This file contains supplementary text, which includes supplementary figures S1-S10 and supplementary table S1.

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Ravetz, B.D., Pun, A.B., Churchill, E.M. et al. Photoredox catalysis using infrared light via triplet fusion upconversion. Nature 565, 343–346 (2019). https://doi.org/10.1038/s41586-018-0835-2

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