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Harvesting singlet and triplet excitation energies in covalent organic frameworks for highly efficient photocatalysis

Nature Materials volume 24, pages 1245–1257 (2025)Cite this article

Abstract

Photocatalysis has traditionally been constrained by selective utilization of either singlet or triplet excited states, limiting efficiency and reaction scope. Achieving simultaneous optimization of both states has remained a challenge. Here we introduce donor–acceptor covalent organic frameworks (COFs) that integrate a dual-state activation strategy. The COFs feature segregated columnar π-arrays, aligned micropores and short donor–acceptor distances. Upon photoexcitation, electron transfer occurs at acceptor units, while energy transfer occurs at donor sites. The porous network also ensures efficient substrate transport to catalytic centres, while intra- and interlayer hydrogen bonding stabilizes excited states, further enhancing photostability and reactivity. This dual-state strategy provides a benchmark for photocatalytic organic transformations, including high turnover frequencies under red-light irradiation, broad-spectrum absorption extending into the near-infrared and operation without metals, co-catalysts or sacrificial donors. By integrating photophysical and structural optimizations, our approach establishes a design strategy that overcomes limitations in solar-driven chemical transformations and broadens the scope of COF-based photocatalysis.

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Fig. 1: Photoexcited states and D–A framework photocatalysts.
Fig. 2: Catalytic process of D–A framework photocatalysts.
Fig. 3: Crystal and porous structures.
Fig. 4: HR-TEM analysis.
Fig. 5: Photophysical properties and reaction intermediates.
Fig. 6: Coupling and condensation reactions with photocatalytic H2P-BT(OMe)2-COF.
Fig. 7: Photocatalytic sites and reaction mechanism.

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Data availability

The data that support the findings of this study are available within the Article and its Supplementary Information. Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2456457 (H2P-BT-COF model compound) and CCDC 2456458 (H2P-BT(OMe)2-COF model compound). Copies of the data can be obtained free of charge at https://www.ccdc.cam.ac.uk. The corresponding CIF files are also provided in Supplementary Data 1–4. Any additional data are available from the corresponding authors upon request. Source data are provided with this paper.

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Acknowledgements

D.J. acknowledges the Singapore MOE Tier 2 grant (T2EP10221-0012) and the Singapore NRF A*STAR grant (U2102d2004). N.Y. thanks the NRF Investigatorship (NRFI07–2021–0015) for financial support. J.L. acknowledges financial support from the National Natural Science Foundation of China (52273208), the Natural Science Foundation of Shanxi Province (202203021211289) and the Research Project supported by the Shanxi Scholarship Council of China (2022-004). We acknowledge Y.G. and X.L. (NUS) for oxygen phosphorescence spectroscopy.

Author information

Author notes

  1. These authors contributed equally: Ruoyang Liu, Dan Zhao.

Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, National University of Singapore, Singapore, Singapore

    Ruoyang Liu, Dan Zhao, Haipei Shao, Yongzhi Chen & Donglin Jiang

  2. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou, China

    Dan Zhao & Tie Wang

  3. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University Katsura, Kyoto, Japan

    Sailun Ji & Shu Seki

  4. Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research (A*STAR), Singapore, Singapore

    Haipei Shao & Ming Lin

  5. Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, Singapore

    Minjun Feng & Tze Chien Sum

  6. Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Singapore

    Tie Wang & Ning Yan

  7. Institute of Crystalline Materials, Shanxi University, Taiyuan, China

    Juan Li

Authors
  1. Ruoyang Liu
  2. Dan Zhao
  3. Sailun Ji
  4. Haipei Shao
  5. Yongzhi Chen
  6. Minjun Feng
  7. Tie Wang
  8. Juan Li
  9. Ming Lin
  10. Tze Chien Sum
  11. Ning Yan
  12. Shu Seki
  13. Donglin Jiang

Contributions

D.J. conceived the idea and led the project. R.L., D.Z. and Y.C. conducted the experiments and measurements. M.F. and T.C.S. conducted and analysed the transient absorption measurements. T.W. and N.Y. conducted the in situ DRIFTS measurements. H.S. and M.L. conducted the HR-TEM measurements. J.L. conducted the nitrogen and acetonitrile sorption measurements. S.J. and S.S. conducted the FP-TRMC measurements. R.L., D.Z., S.J., H.S., Y.C., M.F., T.W., J.L., M.L., T.C.S., N.Y., S.S. and D.J. interpreted the results, and R.L., D.Z. and D.J. wrote the manuscript. All authors have read and commented on the manuscript.

Corresponding author

Correspondence to Donglin Jiang.

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The authors declare no competing interests.

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Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 HR TEM live profile.

a, b, HR TEM live profile of H2P-BT-COF (a) and H2P-BT(OMe)2-COF (b). In the HR TEM live profile of H2P-BT-COF, distances of 4.97 nm and 5.93 nm come from the left side and right side of the porphyrin unit, respectively (a, purple and green arrows), while the benzimidazole unit show distances at 4.16 nm and 6.73 nm (a, blue and orange arrows). Similarly, in H2P-BT(OMe)2-COF, the porphyrin unit exhibits the highest peaks of 4.27 nm and 5.43 nm (b, purple and green arrows), while the 2-methoxy-benzothiadiazole unit shows the lowest peaks of 3.68 nm and 6.2 nm, respectively (b, blue and orange arrows). HR TEM live profiles of both COFs revealed a lower peak between two high peaks, which comes from pore of porphyrin unit. The depth of the troughs suggests discrete spacing between atomic planes, consistent with the porous nature of the COFs.

Source data

Extended Data Fig. 2 Flash-photolysis time resolved microwave conductivity (FP-TRMC) measurements.

a, FP-TRMC transients of H2P-BT-COF under N2 (black), SF6 (red) and Et3N (blue) atmosphere upon excitation at 355 nm. b, FP-TRMC transients of H2P-BT(OMe)2-COF under N2 (black) and SF6 (red) upon excitation at 355 nm. c, FP-TRMC transients of H2P-BT(OMe)2-COF under N2 (black), iodine (red) and Et3N (blue) atmosphere upon excitation at 355 nm. d, Kinetics traces of H2P-BT(OMe)2-COF upon excitation at 266 nm under N2 (red), air (black), NEt3 (blue), NEt3 + N2 (green) and O2 (purple) atmosphere.

Source data

Extended Data Fig. 3 Adsorption features.

a, Acetonitrile sorption isotherms of the COFs (dots: adsorption, circles: desorption; orange: H2P-BT-COF, blue: H2P-BT(OMe)2-COF). b, Radar plot for adsorption comparison of BET surface area, quantity of acetonitrile adsorbed and pore volume between H2P-BT-COF (orange) and H2P-BT(OMe)2-COF (blue). c, d, Charge analysis of benzothidiazole units of H2P-BT-COF (c) and H2P-BT(OMe)2-COF (d). e, f, Electrostatic potential map of H2P-BT-COF (e) and H2P-BT(OMe)2-COF (f) (Red region = negative charge, blue region = positive charge). g, h, Calculated acetonitrile density distribution of H2P-BT-COF (g) and H2P-BT(OMe)2-COF (h) (Red region = low density, blue region = high density). i, l, Calculated average loading of adsorbate per unit cell and average isosteric heats for acetonitrile adsorption (i) and O2 adsorption (l) at 101 kPa. j, k, Calculated oxygen density distribution of H2P-BT-COF (j) and H2P-BT(OMe)2-COF (k) (Orange region = low density, blue region = high density).

Source data

Supplementary information

Supplementary Information

Supplementary Methods, Figs.1–28 and refs.1–61.

Supplementary Data 1

H2P-BT-COF structure in AA-stacking mode.

Supplementary Data 2

H2P-BT(OMe)2-COF structure in AA-stacking mode.

Supplementary Data 3

H2P-BT-COF model compound single-crystal structure.

Supplementary Data 4

H2P-BT(OMe)2-COF model compound single-crystal structure.

Supplementary Data 5

Data for gas chromatographic and NMR analyses of products.

Supplementary Table 1

Single-crystal data of the H2P-BT-COF model compound.

Supplementary Table 2

Unit-cell parameters of COFs.

Supplementary Table 3

Single-crystal data of the H2P-BT(OMe)2-COF model compound.

Supplementary Table 4

Fluorescence lifetime fitting parameters.

Supplementary Table 5

Performance of 1O2 generation.

Supplementary Table 6

Performance comparison of benzylamine oxidative coupling.

Supplementary Table 7

Performance comparison of benzimidazole synthesis.

Supplementary Table 8

Performance comparison of cross-dehydrogenative coupling.

Supplementary Table 9

Control experiments for benzylamine oxidative coupling.

Supplementary Table 10

Control experiments for benzimidazole synthesis.

Supplementary Table 11

Control experiments for cross-dehydrogenative coupling.

Source data

Source Data Fig. 3

PXRD, FTIR and nitrogen adsorption data.

Source Data Fig. 5

UV-visible, Tauc plot, energy level, PDOS, impedance, photocurrent, EPR and degradation of DPBF data.

Source Data Extended Data Fig. 1

HR-TEM live profile data.

Source Data Extended Data Fig. 2

FP-TRMC measurement data.

Source Data Extended Data Fig. 3

Acetonitrile sorption and oxygen sorption, calculated average loading of adsorbate per unit cell and average isosteric heats for acetonitrile adsorption and O2 adsorption data.

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Liu, R., Zhao, D., Ji, S. et al. Harvesting singlet and triplet excitation energies in covalent organic frameworks for highly efficient photocatalysis. Nat. Mater. 24, 1245–1257 (2025). https://doi.org/10.1038/s41563-025-02281-z

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