Abstract
The photochemical [2+2] cycloaddition of styrenes provides a frequently used route for the synthesis of multi-substituted cyclobutanes. Despite the extensive studies in noble-metal and organo-photocatalysis, developing sustainable cycloaddition methods with copper photosensitizers is still in its infancy, largely owing to their low reactivity and photostability. Here we show that the introduction of a binap-ligated heteroleptic copper(I) complex to the linker of a microporous zirconium-based metal−organic framework produces a highly stable and reusable heterogeneous photocatalyst with an extended excited-state lifetime. Under visible light irradiation, this robust copper triplet photosensitizer efficiently promotes multiple intermolecular crossed [2+2] cycloadditions, including an underdeveloped cycloaddition reaction of simple styrenes with electron-deficient alkenes. Our findings suggest that metal–organic framework-based heterogenization strategies have the potential to advance copper photocatalysis and foster a variety of visible light-mediated energy-transfer processes.
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Data availability
The data that support the findings of this study are included in this manuscript and Source data or are available from the corresponding author upon reasonable request. Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2240330 (Cu-1) and 2244329 (Cu-3). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.
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Acknowledgements
The authors thank The University of Hong Kong, the Research Grants Council of the Hong Kong Special Administrative Region, People’s Republic of China (grant nos. 27301820 and 17313922 to J.H., 27200822 and 16302520 to P.C.Y.C., and 15301521 and 15300819 to T.W.B.L.), the Croucher Foundation, the Innovation and Technology Commission (HKSAR, China), and the National Natural Science Foundation of China (grant no. 22201236 to J.H. and 22172136 to T.W.B.L.) for their financial support. The authors thank C.-M. Che for help and discussions.
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J.H. supervised the project and designed the experiments. J.G. developed the photocatalytic cycloadditions and expanded the substrate scope with the help of W.Y.T. Q.X., Z.L. and X.W. prepared and characterized the catalytic materials. L.-J.L. and K.-H.L. analysed the crystal structures of the heteroleptic copper complexes. W.-P.T., H.-X.S. and P.C.Y.C. measured the solid-state emission spectra. T.W.B.L. simulated the EXAFS spectra. J.H. wrote the manuscript with the contributions from J.G., Q.X. and L.-J.L.
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J.H., J.G. and Q.X. are listed as co-inventors of a US patent application, ‘Heterogeneous catalysts and methods making and using thereof’ (63/604,642). The patent describes the synthesis of heterogeneous copper photosensitizers and the photocatalytic performance presented in this manuscript. The remaining authors declare no competing interests.
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Supplementary methods, Figs. 1–45, Tables 1–10 and references.
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Crystallographic data for complex Cu-1.
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Crystallographic data for complex Cu-3.
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Guo, J., Xia, Q., Tang, W.Y. et al. Visible light-mediated intermolecular crossed [2+2] cycloadditions using a MOF-supported copper triplet photosensitizer. Nat Catal 7, 307–320 (2024). https://doi.org/10.1038/s41929-024-01112-9
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DOI: https://doi.org/10.1038/s41929-024-01112-9