Nickel‐Mediated Synthesis of Fused Heterocycle‐Linked Covalent Organic Frameworks for Self‐Sensitized Photocatalysis

Nickel‐Mediated Synthesis of Fused Heterocycle‐Linked Covalent Organic Frameworks for Self‐Sensitized Photocatalysis

Angewandte Chemie International Edition

10.1002/anie.202518983

https://doi.org/10.1002/anie.202518983

Xiaofei Zhang, Yu Tang, Caoyu Yang, Zhenghao Li, Danjun Fu, Lulu Wang, Hoa Phan, Le Yang, Jishan Wu, Jun Zhu

cross-coupling reaction, COFs, Nickel sites

04 November 2025

Zhang, X., Tang, Y., Yang, C., Li, Z., Fu, D., Wang, L., Phan, H., Yang, L., Wu, J., & Zhu, J. (2025). Nickel‐Mediated Synthesis of Fused Heterocycle‐Linked Covalent Organic Frameworks for Self‐Sensitized Photocatalysis. Angewandte Chemie International Edition, 64(52). Portico. https://doi.org/10.1002/anie.202518983

Conjugated and chemically robust covalent organic frameworks (COFs) incorporating metal ions hold great promise in diverse applications due to their finely tuned optoelectronic properties. However, their synthesis typically relies on post-synthetic modifications to stabilize linkages and introduce chelation sites, and metal incorporation is almost exclusively achieved through post-synthetic chelation of pre-formed COFs. Such approaches often result in compromised crystallinity, incomplete conversion and limited control over modification sites. Here, we report a direct, one-pot nickel-mediated Friedländer annulation strategy to construct Ni-chelated fused heterocycle-linked COFs (NNiN, NNiO and NNiS). The fused heterocycle linkages act as an additional structural regulation factor, enabling precise tuning of framework packing and metal-chelation environment, thereby enhancing crystallinity and optoelectronic properties simultaneously. The resulting COFs exhibit extended π-conjugation, efficient Ni chelation and strong charge-transfer absorption in the visible-light region. Combining conjugated robust linkages, accessible single-site Ni centers, and self-photosensitizing capability, these frameworks provide a powerful platform for photocatalysis. They achieved up to 98% conversion in carbon-chalcogen coupling reactions, while retaining crystallinity and catalytic activity over multiple cycles. This work thus offers a general strategy for designing stable, π-conjugated and metal-functionalized COFs, broadening opportunities for heterogeneous catalysis and beyond.

Publisher Copyright

This research / project is supported by the A*STAR - Career Development Fund
Grant Reference no. : C233312013

This research / project is supported by the A*STAR - Manufacturing, Trade, and Connectivity Young Individual Research Grant
Grant Reference no. : M23M7c0118

This research / project is supported by the Ministry of Education - Academic Research Fund Tier 3 program
Grant Reference no. : MOE-000755-00

This research / project is supported by the National Research Foundation - National Research Foundation Fellowship
Grant Reference no. : NRF-NRFF15-2023-0011

This research / project is supported by the A*STAR - Manufacturing, Trade, and Connectivity Programmatic Fund
Grant Reference no. : M24M9b0013

This is the peer reviewed version of the following article: Zhang, X., Tang, Y., Yang, C., Li, Z., Fu, D., Wang, L., Phan, H., Yang, L., Wu, J., & Zhu, J. (2025). Nickel‐Mediated Synthesis of Fused Heterocycle‐Linked Covalent Organic Frameworks for Self‐Sensitized Photocatalysis. Angewandte Chemie International Edition, 64(52). Portico. https://doi.org/10.1002/anie.202518983, which has been published in final form at https://doi.org/10.1002/anie.202518983. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.

https://oar.a-star.edu.sg/communities-collections/articles/22843

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Institute of Materials Research and Engineering