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Metallaphotocatalytic Amination of Aryl Chlorides Enabled by Highly Crystalline Acetylene-Based Hydrazone-Linked Covalent Organic Frameworks |
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| Authors: | Yusran Yusran Jiabin Xing Qihan Lin Gang Wu Wen-Chang Peng Yan Wu Tianhui Su Lingyi Yang Liming Zhang Qiaowei Li Hui Wang Zhan-Ting Li Dan-Wei Zhang |
| Affiliation: | 1. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 2005 Songhu Road, Shanghai, 200438 P. R. China;2. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 2005 Songhu Road, Shanghai, 200438 P. R. China Contribution: Formal analysis (supporting), Investigation (supporting), Methodology (supporting);3. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 2005 Songhu Road, Shanghai, 200438 P. R. China Contribution: Formal analysis (supporting), Methodology (supporting), Writing - review & editing (supporting);4. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 2005 Songhu Road, Shanghai, 200438 P. R. China Contribution: Investigation (supporting), Methodology (supporting), Writing - review & editing (supporting);5. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 2005 Songhu Road, Shanghai, 200438 P. R. China Contribution: Investigation (supporting), Methodology (supporting);6. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 2005 Songhu Road, Shanghai, 200438 P. R. China Contribution: Formal analysis (supporting), Resources (supporting), Software (supporting);7. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 2005 Songhu Road, Shanghai, 200438 P. R. China Contribution: Methodology (supporting), Resources (supporting), Software (supporting);8. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 2005 Songhu Road, Shanghai, 200438 P. R. China Contribution: Methodology (supporting), Project administration (supporting), Resources (supporting), Supervision (supporting);9. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 2005 Songhu Road, Shanghai, 200438 P. R. China Contribution: Conceptualization (supporting), Formal analysis (supporting), Funding acquisition (equal), Investigation (supporting), Methodology (supporting), Project administration (supporting), Resources (equal), Supervision (supporting), Validation (supporting), Writing - original draft (supporting), Writing - review & editing (supporting) |
| Abstract: | Amination of aryl chlorides by metallaphotocatalysis is highly desired but remains practically challenging. Meanwhile, relying on soluble noble-metal photocatalysts suffers from resource scarcity and structural instability which limit their practical application. Here in, a highly crystalline acetylene-based hydrazone-linked covalent organic framewok-1 (AC-COF-1) is reported that enables metallaphotocatalytic amination of aryl chlorides. The non-planar effect of hydrazone linkage and weak interlayer attraction of acetylene bond are minimized by intralayer hydrogen-bonding. As a result, the COF shows not only improved crystallinity and porosity, but also enhanced optical and electronic properties compared to a COF analog without hydrogen-bonding. Notably, dual AC-COF-1 /Ni system affords C N coupling products from broad aryl chloride substrates in excellent yields (up to 99%) and good functional tolerance. Furthermore, AC-COF-1 is recoverable and reusable for seven times photocatalysis cycles. This report demonstrates simple approach to tune the structure-activity relationship in COFs at molecular level. |
| Keywords: | aryl chlorides covalent organic frameworks metallaphotocatalysis Ni catalysis photocatalysis |