Anthraquinone-based covalent organic framework as a recyclable direct hydrogen atom transfer photocatalyst for C–H functionalization

Wang, Zitong; Yeary, Pierce; Fan, Yingjie; Lin, Wenbin

doi:10.1039/d4sc00241e

Chem. Sci.

2024

DOI: 10.1039/d4sc00241e

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Anthraquinone-based covalent organic framework as a recyclable direct hydrogen atom transfer photocatalyst for C–H functionalization

Zitong Wang,

Pierce Yeary,

Yingjie Fan

et al.

Abstract: Photocatalytic direct hydrogen atom transfer (d-HAT) is a synthetically important strategy to convert C-H bonds to useful C-X bonds. Herein we report the synthesis of an anthraquinone-based two-dimensional covalent organic...

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Cited by 6 publications

References 63 publications

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Visible‐Light‐Mediated Selective Fluorine Incorporation by Anthraquinone‐Based Covalent Organic Framework as Recyclable Photocatalyst

Jati,

Das,

Shukla

et al. 2024

ChemCatChem

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Covalent organic frameworks (COFs) serve as an excellent foundation for heterogeneous photocatalysis. Herein, we synthesized an anthraquinone‐based COF (TpAQ) on a gram scale via a mechanochemical grinding pathway. This COF was employed as a visible‐light‐harvesting photocatalyst for selective fluorination of benzylic C‐H bonds and perfluoroalkylation of arenes. The carbonyl core in the anthraquinone linker facilitated benzylic fluorination through a hydrogen atom transfer (HAT) pathway. Control experiments and photophysical analysis were conducted to gain deeper insight into the reaction mechanism. The recyclability up to 5th cycle without significant loss of the yield (> 90%) highlighted the robustness of the catalyst. This reaction strategy was also executed on a gram scale to validate the scalability of the protocol.

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Visible‐Light‐Mediated Selective Fluorine Incorporation by Anthraquinone‐Based Covalent Organic Framework as Recyclable Photocatalyst

Jati,

Das,

Shukla

et al. 2024

ChemCatChem

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Multifunctional Polyoxovanadate-Based Covalent Organic Polymer for Bacteria-Infected Wound Therapy

Li,

Zhao,

Liu

et al. 2024

ACS Appl. Nano Mater.

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The special pathological microenvironment of infected wounds (pathology of weakly acidic, hypoxic, and overexpressed H 2 O 2 ) provides fertile soil for the development of disease. Tailoring treatment based on the specific characteristics of the infectious microenvironment (IME) has emerged as a novel direction in the development of antimicrobial therapies. Here, a polyoxovanadate (POV)-based covalent organic polymer (POV-Fc-COP) with inherent photothermal activity was facilely prepared via the copolymerization of 1,1′-bi(3-dimethylamino-1-oxo-2-enylferrocene) (BDOEF) with tris-NH 2 -modified POV (tris-V 6 O 9 ), in which the nanovanadium oxide (V 2 O 3 and V 2 O 5 ) core and polymer shell were generated directly during the Michael addition−elimination reaction. The unique structure and composition impart pH-responsive peroxidase-like (POD-like) and catalase-like (CAT-like) activities, concurrently, to the POV-Fc-COP. Specifically, the acid-activated mimicking-POD activity could consume H 2 O 2 in the microenvironment, producing toxic •OH to combat bacteria and biofilms. The vanadium oxide consumes the excessive acid, resulting in an increase in pH. Meanwhile, the CATlike activity could transform excess H 2 O 2 expression into O 2 to relieve hypoxia induced by the damage of blood vessels in the wounds and facilitate wound healing. Additionally, the synergistic amplified therapeutic effect triggered by the application of laser irradiation facilitates the rapid eradication of bacteria and biofilm, minimizing the detrimental impacts of bacterial proliferation on the IME, thereby accelerating the restoration of the IME return to a normal state. Therefore, POV-Fc-COP with a dual-enzyme functionality could not only utilize but also regulate the IME, significantly expediting the healing of bacteria-infected wounds. This study demonstrates a simple method for the preparation of an intelligent platform for programmed antibacterial and antibiofilm formation, thus promoting healing while utilizing and improving the IME.

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Photocatalytic Decarboxylative Fluorination by Quinone-Based Isoreticular Covalent Organic Frameworks

Jati,

Mahato,

Chanda

et al. 2024

J. Am. Chem. Soc.

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The strategic incorporation of fluorine atoms into molecules has become a cornerstone of modern pharmaceuticals, agrochemicals, and materials science. Herein, we have developed a covalent organic framework (COF)-based, robust photocatalyst that enables the photofluorodecarboxylation reaction of diverse carboxylic acids, producing alkyl fluorides with remarkable efficiency. The catalytic activity of an anthraquinone-based COF catalyst TpAQ outperforms other structurally analogous β-ketoenamine COFs. Through comprehensive control experiments, photoluminescence, and electrochemical studies, we have elucidated the unique features of the material and the mechanistic pathway. This in-depth understanding has paved the way for optimizing the reaction conditions and achieving high yields of alkyl fluorides. The versatility of this protocol extends to a broad range of aliphatic acids with diverse functional groups and heterocycles. It also enabled the late-stage diversification of anti-inflammatory drugs and steroid derivatives. This opens up exciting possibilities for synthesizing novel pharmaceuticals and functionalized molecules. The methodology was also generalized to other light-mediated decarboxylative halogenation reactions. Furthermore, our method demonstrates scalability under both batch and continuous flow conditions, offering a promising approach for large-scale production. Additionally, the TpAQ catalyst exhibits exceptional durability and can be reused multiple times without significant activity loss (>80% yield after the eighth cycle), making it a sustainable and cost-effective solution. This work lays the foundation for developing efficient and sustainable light-driven synthesis methods using COFs as photocatalysts with potential applications beyond alkyl halide synthesis.

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Anthraquinone-based covalent organic framework as a recyclable direct hydrogen atom transfer photocatalyst for C–H functionalization

Abstract: Photocatalytic direct hydrogen atom transfer (d-HAT) is a synthetically important strategy to convert C-H bonds to useful C-X bonds. Herein we report the synthesis of an anthraquinone-based two-dimensional covalent organic...

Cited by 6 publications

References 63 publications

Visible‐Light‐Mediated Selective Fluorine Incorporation by Anthraquinone‐Based Covalent Organic Framework as Recyclable Photocatalyst

Visible‐Light‐Mediated Selective Fluorine Incorporation by Anthraquinone‐Based Covalent Organic Framework as Recyclable Photocatalyst

Multifunctional Polyoxovanadate-Based Covalent Organic Polymer for Bacteria-Infected Wound Therapy

Photocatalytic Decarboxylative Fluorination by Quinone-Based Isoreticular Covalent Organic Frameworks

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