Flexible three-dimensional diacetylene functionalized covalent organic frameworks for efficient iodine capture

Zou, Junyan; Wen, Dan; Zhao, Yu

doi:10.1039/d2dt03362c

Cited by 9 publications

(8 citation statements)

References 62 publications

(38 reference statements)

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“…In conclusion, the insertion of acetylenes from TMT-TFPB-COF to TMT-TFPEB-COF eliminates the steric effect and provides more delocalized π-electrons, inducing extended visible-light absorption, high charge mobility, and suppressed charge recombination. The superiority of acetylene groups in extending visible-light response and suppressing charge recombination rate has been revealed. − It seems that the insertion of diacetylene could induce more considerable promotion of the optical properties of COFs. , Here, the insertion of diacetylenes into TMT-TFPB-COF was attempted to further explore the effect of expanding the π-conjugation on the photocatalytic performance. However, these endeavors were fruitless in affording crystalline materials, even after dozens of attempts.…”

Section: Results and Discussionmentioning

confidence: 99%

Expanding Olefin-Linked Covalent Organic Frameworks toward Selective Photocatalytic Oxidation of Organic Sulfides

Zhang,

Wang,

Zhao

et al. 2024

ACS Appl. Mater. Interfaces

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Olefin-linked covalent organic frameworks (COFs) have exhibited great potential in visible-light photocatalysis. In principle, expanding fully conjugated COFs can facilitate light absorption and charge transfer, leading to improved photocatalysis. Herein, three olefin-linked COFs with the same topology are synthesized by combining 2,4,6-trimethyl-1,3,5-triazine (TMT) with 1,3,5-triformylbenzene (TFB), 1,3,5-tris(4-formylphenyl)benzene (TFPB), and 1,3,5-tris(4-formylphenylethynyl)benzene (TFPEB), namely, TMT-TFB-COF, TMT-TFPB-COF, and TMT-TFPEB-COF, respectively. From TMT-TFB-COF to TMT-TFPB-COF, expanding phenyl rings provides only limited expansion for π-conjugation due to the steric effect of structural twisting. However, from TMT-TFPB-COF to TMT-TFPEB-COF, the insertion of acetylenes eliminates the steric effect and provides more delocalized π-electrons. As such, TMT-TFPEB-COF exhibits the best optoelectronic properties among these three olefin-linked COFs. Consequently, the photocatalytic performance of TMT-TFPEB-COF is much better than those of TMT-TFB-COF and TMT-TFPB-COF on the oxidation of organic sulfides into sulfoxides with oxygen. The desirable reusability and substrate compatibility of the TMT-TFPEB-COF photocatalyst are further confirmed. The selective formation of organic sulfoxides over TMT-TFPEB-COF under blue light irradiation proceeds via both electron-and energy-transfer pathways. This work highlights a rational design of expanding the π-conjugation of fully conjugated COFs toward selective visible-light photocatalysis.

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Section: Results and Discussionmentioning

confidence: 99%

Expanding Olefin-Linked Covalent Organic Frameworks toward Selective Photocatalytic Oxidation of Organic Sulfides

Zhang,

Wang,

Zhao

et al. 2024

ACS Appl. Mater. Interfaces

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“…Zhao et al reported that CPOF-2 and CPOF-3 functionalized with electron-rich acetylene and diacetylene groups exhibited high adsorption capacities of 5.40 and 5.87 g g −1 , respectively. 89 Fang et al also demonstrated a strong interaction between tetrathiafulvalene (TTF) and I 2 in JUC-561 with an excellent uptake of 8.19 g g −1 . 90…”

Section: Gas Storagementioning

confidence: 98%

Reticular chemistry within three-dimensional covalent organic frameworks for multiple applications

Wang,

Gao,

Kang

et al. 2023

J. Mater. Chem. A

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“…13 C NMR (126 MHz, CDCl 3 ):  = 93.3, 90.1, -0.2. 70 Yield: 160 mg (81%); pale yellow solid; mp 119-120 °C. R f = 0.44 (20% EtOAc/n-hexane).…”

Section: 4′-(buta-13-diyne-14-diyl)bis(nn-dimethylaniline) (2h)mentioning

confidence: 99%

“…4′-(Buta-1,3-diyne-1,4-diyl)dibenzaldehyde (2o)70 Yield: 160 mg (81%); pale yellow solid; mp 119-120 °C. R f = 0.44 (20% EtOAc/n-hexane).…”

mentioning

confidence: 99%

Synthetic Access to 1,3-Butadiynes via Electro-redox Cuprous-Catalyzed Dehydrogenative Csp–Csp Homocoupling of Terminal Acetylenes

Kathiresan,

Praveen,

Krishnan

2023

Synthesis

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Herein, we disclose the oxidative homocoupling of terminal alkynes under electrochemically generated cuprous catalysis. The scope of this protocol was established by preparing an array of structurally and electronically different 1,3-butadiyne derivatives. Good synthetic yields, functional group tolerance, oxidant-free conditions, and no cross-selectivity are some of the intrinsic advantages of this methodology. The developed chemistry features the electro-redox formation of copper acetylide, an intermediate appropriate for the Csp–Csp coupling step. The chemical state of copper in the acetylide intermediate was found to be Cu(I), as confirmed by click trapping experiments, cyclic voltammetry, EPR spectroscopy, and XPS. A competition reaction to determine the reactivity of electronically dissimilar acetylenes revealed that the product ratio is rather dependent on the electronic nature of the alkynyl substituents. To highlight the synthetic value of the products, selected diynes were subjected to chemical diversification.

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Flexible three-dimensional diacetylene functionalized covalent organic frameworks for efficient iodine capture

Abstract: The construction of functionalized covalent organic frameworks (COFs) is of great significance for broadening their potential applications, but are yet challenging to achieve, especially to three-dimensional (3D) COFs, because the...

Cited by 9 publications

References 62 publications

Expanding Olefin-Linked Covalent Organic Frameworks toward Selective Photocatalytic Oxidation of Organic Sulfides

Expanding Olefin-Linked Covalent Organic Frameworks toward Selective Photocatalytic Oxidation of Organic Sulfides

Reticular chemistry within three-dimensional covalent organic frameworks for multiple applications

Synthetic Access to 1,3-Butadiynes via Electro-redox Cuprous-Catalyzed Dehydrogenative Csp–Csp Homocoupling of Terminal Acetylenes

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