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

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

Nature Materials

10.1038/s41563-025-02281-z

https://doi.org/10.1038/s41563-025-02281-z

Ruoyang Liu, Dan Zhao, Sailun Ji, Haipei Shao, Yongzhi Chen, Minjun Feng, Tie Wang, Juan Li, Ming Lin, Tze Chien Sum, Ning Yan, Shu Seki, Donglin Jiang

Covalent organic frameworks, Photocatalysis

16 July 2025

Liu, R., Zhao, D., Ji, S., Shao, H., Chen, Y., Feng, M., Wang, T., Li, J., Lin, M., Sum, T. C., Yan, N., Seki, S., & Jiang, D. (2025). Harvesting singlet and triplet excitation energies in covalent organic frameworks for highly efficient photocatalysis. Nature Materials, 24(8), 1245–1257. https://doi.org/10.1038/s41563-025-02281-z

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.

Publisher Copyright

This research / project is supported by the Ministry of Education, Singapore - Academic Research Fund Tier 2
Grant Reference no. : T2EP10221-0012

This research / project is supported by the National Research Foundation, A*STAR - NA
Grant Reference no. : U2102d2004

This research / project is supported by the National Research Foundation - National Research Foundation Investigatorship
Grant Reference no. : NRFI07–2021–0015

This research / project is supported by the National Natural Science Foundation of China - NA
Grant Reference no. : 52273208

This research / project is supported by the Natural Science Foundation of Shanxi Province, china - NA
Grant Reference no. : 202203021211289

This is a post-peer-review, pre-copyedit version of an article published in Nature Materials. The final authenticated version is available online at: http://dx.doi.org/10.1038/s41563-025-02281-z.

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