Construction of Covalent Organic Frameworks via a Visible-Light-Activated Photocatalytic Multicomponent Reaction

Wang, Guang-Bo; Wang, Yanjing; Kan, Jing‐Lan; Xie, Ke-Hui; Xu, Hai-Peng; Zhao, Fei; Wang, Miao-Can; Geng, Yanfang; Dong, Yu‐Bin

doi:10.1021/jacs.2c13541

Cited by 66 publications

(33 citation statements)

References 52 publications

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“…Furthermore, a broad scope of substrates could be catalyzed by the dimer. This is similar to other catalysts that could work with a broad scope of substrates (Figure B). − …”

Section: Resultssupporting

confidence: 83%

Employing Singlet Fission into Boosting the Generation of Singlet Oxygen and Superoxide Radicals for Photooxidation Reactions

Wang,

Liu,

Wang

et al. 2023

ACS Catal.

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Developing highly efficient heavy-metal-free photosensitizers (PSs) for the production of reactive oxygen species (ROS) is urgent to achieve wide applications of ROS, yet it remains a great challenge. As a proof of concept, singlet fission (SF), possessing the exciton multiplication ability with a maximum 200% triplet yield, is employed to generate ROS. Herein, a metal-free tetracene dimer with a high yield (∼164%) of long-lived triplets (>300 μs) is prepared and used to generate singlet oxygen (1O2) and superoxide radicals (O2 ·–). Remarkably, 1O2 and O2 ·– yields are boosted compared to the existing traditional PSs based on intersystem crossing (ISC). The 1O2 yield reaches an unprecedented ∼148%, representing the highest value ever reported so far. Thus, this SF PS shows an improved photooxidation activity over ISC PSs. Additionally, the 1O2 and O2 ·– generation mechanisms are described clearly by combining TA spectra and controlled experiments. This represents the first example of utilizing the two triplet states produced by SF to generate ROS and catalyze related reactions. The work not only presents a strategy for generating and enhancing the 1O2/O2 ·– yield but also opens up a new field for the application of SF.

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“…Furthermore, a broad scope of substrates could be catalyzed by the dimer. This is similar to other catalysts that could work with a broad scope of substrates (Figure B). − …”

Section: Resultssupporting

confidence: 83%

Employing Singlet Fission into Boosting the Generation of Singlet Oxygen and Superoxide Radicals for Photooxidation Reactions

Wang,

Liu,

Wang

et al. 2023

ACS Catal.

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“…To confirm the formation of imine linkages in NJU-318 and NJU-319Fe, Fourier transform infrared (FTIR) spectra and solid-state nuclear magnetic resonance (ssNMR) spectra were collected (Figures S4–S7). The diminished CO stretching vibration at 1701 cm –1 of the aldehydes and the appearance of characteristic CN stretching vibrations at 1625 cm –1 for NJU-318 and NJU-319Fe corroborated the formation of imine bonds. − Furthermore, the CN peaks (158 ppm for NJU-318 and 159 ppm for NJU-319Fe) in the ssNMR spectra further verified the existence of imine groups in both NJU-318 and NJU-319Fe.…”

Section: Resultsmentioning

confidence: 69%

Postsynthetic Annulation of Three-Dimensional Covalent Organic Frameworks for Boosting CO₂ Photoreduction

Dong

Luo

et al. 2023

J. Am. Chem. Soc.

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Three-dimensional covalent organic frameworks (3D COFs), with interconnected pores and exposed functional groups, provide new opportunities for the design of advanced functional materials through postsynthetic modification. Herein, we demonstrate the successful postsynthetic annulation of 3D COFs to construct efficient CO2 reduction photocatalysts. Two 3D COFs, NJU-318 and NJU-319Fe, were initially constructed by connecting hexaphenyl-triphenylene units with pyrene- or Fe-porphyrin-based linkers. Subsequently, the hexaphenyl-triphenylene moieties within the COFs were postsynthetically transformed into π-conjugated hexabenzo-trinaphthylene (pNJU-318 and pNJU-319Fe) to enhance visible light absorption and CO2 photoreduction activity. The optimized photocatalyst, pNJU-319Fe, shows a CO yield of 688 μmol g–1, representing a 2.5-fold increase compared to that of unmodified NJU-319Fe. Notably, the direct synthesis of hexabenzo-trinaphthylene-based COF catalysts was unsuccessful due to the low solubility of conjugated linkers. This study not only provides an effective method to construct photocatalysts but also highlights the unlimited tunability of 3D COFs through structural design and postsynthetic modification.

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“…[26] In 2023, Dong et al reported the synthesis of a series of COFs via photocatalytic multicomponent Petasis reaction under visible light irradiation (Figure 8). [27] In the presence of [Ir-(dtbbpy)(ppy) 2 ]PF 6 as the photosensitizer, four different COFs with excellent crystallinity, stability, and permanent porosity termed as Cy-N 3 -COF, Cy-LZU-1, Cy-COF-42, and Cy-TPB-DMTP-COF were constructed via the condensation of potassium cyclohexyltrifluoroborate with different aldehydes and hydrazines or amines or hydrazides using acetic acid as the catalyst in anhydrous 1,4-dioxane under blue LED irradiation for 72 h at room temperature. Furthermore, the obtained Cy-N 3 -COF exhibited excellent photoactivity and recyclability for the photocatalytic oxidative hydroxylation of arylboronic acids with a wide substrate scope.…”

Section: Photocatalytic Reaction Using a Photocatalystmentioning

confidence: 99%

Photochemical Synthesis of Covalent Organic Frameworks

Shao

Geng

et al. 2023

ChemCatChem

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As a booming class of crystalline porous materials, covalent organic frameworks (COFs) have attracted increasing attention and various methods to construct COFs have been investigated including solvothermal synthesis, ionothermal synthesis, microwave synthesis, mechanical synthesis, sonochemical synthesis, interfacial synthesis, and electrochemical synthesis. Recently, photochemical reaction has emerged as a powerful approach for COF synthesis, which utilizing the non‐toxic, abundant and renewable light as the energy source. Benefitting from its outstanding properties of low‐cost, safety, and environmental friendliness, the photochemical reaction was considered as a promising alternative to the conventional thermal reaction for COF synthesis. In this concept article, we summarized the up‐to‐date reports about the photochemical synthesis of COFs and provided a future perspective in this field. It is anticipated that this concept could be beneficial for the further development of photochemical synthesis of COFs.

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Construction of Covalent Organic Frameworks via a Visible-Light-Activated Photocatalytic Multicomponent Reaction

Cited by 66 publications

References 52 publications

Employing Singlet Fission into Boosting the Generation of Singlet Oxygen and Superoxide Radicals for Photooxidation Reactions

Employing Singlet Fission into Boosting the Generation of Singlet Oxygen and Superoxide Radicals for Photooxidation Reactions

Postsynthetic Annulation of Three-Dimensional Covalent Organic Frameworks for Boosting CO₂ Photoreduction

Photochemical Synthesis of Covalent Organic Frameworks

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Construction of Covalent Organic Frameworks via a Visible-Light-Activated Photocatalytic Multicomponent Reaction

Cited by 66 publications

References 52 publications

Employing Singlet Fission into Boosting the Generation of Singlet Oxygen and Superoxide Radicals for Photooxidation Reactions

Employing Singlet Fission into Boosting the Generation of Singlet Oxygen and Superoxide Radicals for Photooxidation Reactions

Postsynthetic Annulation of Three-Dimensional Covalent Organic Frameworks for Boosting CO2 Photoreduction

Photochemical Synthesis of Covalent Organic Frameworks

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Postsynthetic Annulation of Three-Dimensional Covalent Organic Frameworks for Boosting CO₂ Photoreduction