Facile construction of olefin-linked covalent organic frameworks for enhanced photocatalytic organic transformation <i>via</i> wall surface engineering

Cai, Kairui; Wang, Wenjing; Zhang, Jie; Chen, Lei; Wang, Lianke; Zhu, Xiaojiao; Yu, Zhipeng; Wu, Zhichao; Zhou, Hongping

doi:10.1039/d1ta09684b

Cited by 25 publications

(14 citation statements)

References 48 publications

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“…The energy levels of the VB can then be calculated using the equation: 5c). 37 To perform the targeted Povarov reaction, the amines of the glycine esters need to be oxidized and oxygen-reduced. The reduction potential of O 2 is −0.62 V (vs NHE) 38 and the oxidation potentials for a representative N-aryl glycine ester, ethyl ptolylglycinate, is 1.30 V (vs NHE).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Engineering of Phenylpyridine- and Bipyridine-Based Covalent Organic Frameworks for Photocatalytic Tandem Aerobic Oxidation/Povarov Cyclization

Debruyne

Borgmans

Radhakrishnan

et al. 2023

ACS Appl. Mater. Interfaces

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Covalent organic frameworks (COFs) are emerging as a new class of photoactive organic semiconductors, which possess crystalline ordered structures and high surface areas. COFs can be tailor-made toward specific (photocatalytic) applications, and the size and position of their band gaps can be tuned by the choice of building blocks and linkages. However, many types of building blocks are still unexplored as photocatalytic moieties and the scope of reactions photocatalyzed by COFs remains quite limited. In this work, we report the synthesis and application of two bipyridine- or phenylpyridine-based COFs: TpBpyCOF and TpPpyCOF. Due to their good photocatalytic properties, both materials were applied as metal-free photocatalysts for the tandem aerobic oxidation/Povarov cyclization and α-oxidation of N-aryl glycine derivatives, with the bipyridine-based TpBpyCOF exhibiting the highest activity. By expanding the range of reactions that can be photocatalyzed by COFs, this work paves the way toward the more widespread application of COFs as metal-free heterogeneous photocatalysts as a convenient alternative for commonly used homogeneous (metal-based) photocatalysts.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Engineering of Phenylpyridine- and Bipyridine-Based Covalent Organic Frameworks for Photocatalytic Tandem Aerobic Oxidation/Povarov Cyclization

Debruyne

Borgmans

Radhakrishnan

et al. 2023

ACS Appl. Mater. Interfaces

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“…[154] Finally, a series of olefin-linked COFs obtained from the combination of trimetyltriazine and different trigonal ortho-substituted aldehydes was obtained by Zhou and co-workers (Figure 10). [155] Depending on the substituents in the ortho-position of the aldehyde building block, the photophysical properties of the materials were modified. For example, in the presence of a methoxy group, a wider visible-light absorption and better transfer efficiency were observed.…”

Section: Aryl Boronic Acid Oxidation Reactionsmentioning

confidence: 99%

Recent Advances in the Use of Covalent Organic Frameworks as Heterogenous Photocatalysts in Organic Synthesis

et al. 2023

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Organic photochemistry is intensely developed in the 1980s, in which the nature of excited electronic states and the energy and electron transfer processes are thoroughly studied and finally well‐understood. This knowledge from molecular organic photochemistry can be transferred to the design of covalent organic frameworks (COFs) as active visible‐light photocatalysts. COFs constitute a new class of crystalline porous materials with substantial application potentials. Featured with outstanding structural tunability, large porosity, high surface area, excellent stability, and unique photoelectronic properties, COFs are studied as potential candidates in various research areas (e.g., photocatalysis). This review aims to provide the state‐of‐the‐art insights into the design of COF photocatalysts (pristine, functionalized, and hybrid COFs) for organic transformations. The catalytic reaction mechanism of COF‐based photocatalysts and the influence of dimensionality and crystallinity on heterogenous photocatalysis performance are also discussed, followed by perspectives and prospects on the main challenges and opportunities in future research of COFs and COF‐based photocatalysts.

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“…They feature adjustability of porosity, high stability, and excellent photocatalytic performance and presented enormous potential in various fields including gas adsorption and separation, − sensing, − biomedicine, − energy storage, − optoelectronics, − and catalysis. − Especially, due to the characteristics of the regular pore structure, quite stability, the extended π-conjugated framework have particularly extensive application as photocatalysts. , However, most of these COFs based on imine, cyanogene, or β-ketoenamine linkers limited the light absorption, charge separation, as well as stability of the materials. , Under the premise, vinylene-linked COFs developed may enable efficient photocatalytic organic reactions . Recently, some groups used olefin-linked COFs as photocatalysts for photocatalytic organic reaction conversion. ,− However, the correlation of the COFs’ structure with their photophysical properties and photocatalytic activity is still not clear …”

Section: Introductionmentioning

confidence: 99%

Nanoporous Vinylene-Linked 2D Covalent Organic Frameworks for Visible-Light-Driven Aerobic Oxidation

Wang

Cai

Zhou

et al. 2023

ACS Appl. Nano Mater.

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Exploring vinylene-linked nanoporous covalent organic framework (COF) materials has become a valuable research focus due to their various outstanding properties. However, only a few examples have been reported to construct vinylene-linked COFs, which seriously restricted their applications. Herein, two COFs linked by olefins TC-PT and TC-PB via the Knoevenagel condensation of 1,3,5-tris(4-cyanomethylphenyl) benzene and 2,4,6-tris (4-formylphenyl)-1,3,5-triazine or 1,3,5-tris (4-formylphenyl) benzene were designed and constructed, which possessed high crystallinity, remarkable porosity, and high structural, chemical, and thermal stability. The two nanoporous organic framework materials prepared can be used for catalytic organic reaction of phenylboric acid and its derivatives driven efficiently by visible light. It is noted that TC-PT with a donor–acceptor structure presented excellent activity, yield, and recyclability. We believed that this work would provide some precious insights for developing functional vinylene-linked COFs.

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Facile construction of olefin-linked covalent organic frameworks for enhanced photocatalytic organic transformation via wall surface engineering

Abstract: Exploration of fully conjugated covalent organic frameworks (COFs)-based photocatalyst has become valuable research owing to the excellent stability, outstanding semiconducting properties and fascinating properties. However, the design and construction of...

Cited by 25 publications

References 48 publications

Engineering of Phenylpyridine- and Bipyridine-Based Covalent Organic Frameworks for Photocatalytic Tandem Aerobic Oxidation/Povarov Cyclization

Engineering of Phenylpyridine- and Bipyridine-Based Covalent Organic Frameworks for Photocatalytic Tandem Aerobic Oxidation/Povarov Cyclization

Recent Advances in the Use of Covalent Organic Frameworks as Heterogenous Photocatalysts in Organic Synthesis

Nanoporous Vinylene-Linked 2D Covalent Organic Frameworks for Visible-Light-Driven Aerobic Oxidation

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