Chalcogen-bridged coordination polymer for the photocatalytic activation of aryl halides

Le Zeng, Tiexin Zhang (), Renhai Liu, Wenming Tian, Kaifeng Wu, Jingyi Zhu, Zhonghe Wang, Cheng He, Jing Feng, Xiangyang Guo, Abdoulkader Ibro Douka and Chunying Duan ()
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Le Zeng: Dalian University of Technology
Tiexin Zhang: Dalian University of Technology
Renhai Liu: Dalian University of Technology
Wenming Tian: Chinese Academy of Sciences
Kaifeng Wu: Chinese Academy of Sciences
Jingyi Zhu: Chinese Academy of Sciences
Zhonghe Wang: Dalian University of Technology
Cheng He: Dalian University of Technology
Jing Feng: Dalian University of Technology
Xiangyang Guo: Chinese Academy of Sciences
Abdoulkader Ibro Douka: Dalian University of Technology
Chunying Duan: Dalian University of Technology

Nature Communications, 2023, vol. 14, issue 1, 1-13

Abstract: Abstract The ability to deliver electrons is vital for dye-based photocatalysts. Conventionally, the aromatic stacking-based charge-transfer complex increases photogenerated electron accessibility but decreases the energy of excited-state dyes. To circumvent this dilemma, here we show a strategy by tuning the stacking mode of dyes. By decorating naphthalene diimide with S-bearing branches, the S···S contact-linked naphthalene diimide string is created in coordination polymer, thereby enhancing electron mobility while simultaneously preserving competent excited-state reducing power. This benefit, along with in situ assembly between naphthalene diimide strings and exogenous reagent/reactant, improves the accessibility of short-lived excited states during consecutive photon excitation, resulting in greater efficiency in photoinduced electron-transfer activation of inert bonds in comparison to other coordination polymers with different dye-stacking modes. This heterogeneous approach is successfully applied in the photoreduction of inert aryl halides and the successive formation of CAr−C/S/P/B bonds with potential pharmaceutical applications.

Date: 2023
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DOI: 10.1038/s41467-023-39540-z

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