All sp2 carbon covalent organic frameworks

He, Ting; Geng, Keyu; Jiang, Donglin

doi:10.1016/j.trechm.2021.03.008

Cited by 85 publications

(70 citation statements)

References 57 publications

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“…[5] However, the synthesis of high-quality sp 2 -carbon frameworks is still limited in terms of structural accessibility and diversity. [6] In this study, we report a module-patterned polymerization approach to synthesize crystalline porous COFs based on the C=C bond-formation reaction. Remarkably, we observed that a four-branched C 2 -symmetryic knot enables a module-patterned polymerization to produce crystalline porous sp 2 -carbon COFs.…”

Section: Introductionmentioning

confidence: 99%

Module‐Patterned Polymerization towards Crystalline 2D sp²‐Carbon Covalent Organic Framework Semiconductors

et al. 2022

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Despite rapid progress over the past decade, most polycondensation systems even upon a small structural variation of the building units eventually result in amorphous polymers other than the desired crystalline covalent organic frameworks. This synthetic dilemma is a central and challenging issue of the field. Here we report a novel approach based on module‐patterned polymerization to enable efficient and designed synthesis of crystalline porous polymeric frameworks. This strategy features a wide applicability to allow the use of various knots of different structures, enables polycondensation with diverse linkers, and develops a diversity of novel crystalline 2D polymers and frameworks, as demonstrated by using the C=C bond‐formation polycondensation reaction. The new sp2‐carbon frameworks are highly emissive and enable up‐conversion luminescence, offer low band gap semiconductors with tunable band structures, and achieve ultrahigh charge mobilities close to theoretically predicted maxima.

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Section: Introductionmentioning

confidence: 99%

Module‐Patterned Polymerization towards Crystalline 2D sp²‐Carbon Covalent Organic Framework Semiconductors

et al. 2022

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“…Vinylene‐linked 2D covalent organic frameworks (V‐2D‐COFs, or vinylene‐linked 2D conjugated polymers) have recently attracted arising attention because of the robust and superb π‐conjugated framework structures with high chemical stability [24–29] . Several synthetic methodologies, including Knoevenagel‐, [24, 25] other Aldol‐type‐, [29–32] and Horner–Wadsworth–Emmons [19] based 2D polycondensation approaches, have been developed.…”

Section: Introductionmentioning

confidence: 99%

“…[22,23] Vinylene-linked 2D covalent organic frameworks (V-2D-COFs, or vinylene-linked 2D conjugated polymers) have recently attracted arising attention because of the robust and superb π-conjugated framework structures with high chemical stability. [24][25][26][27][28][29] Several synthetic methodologies, including Knoevenagel-, [24,25] other Aldol-type-, [29][30][31][32] and Horner-Wadsworth-Emmons [19] based 2D polycondensation approaches, have been developed. Particularly, several CNsubstituted V-2D-COFs have been successfully synthesized via Knoevenagel polycondensation, and demonstrated superior performance as magnetic materials, [25] organic cathodes for lithium-ion batteries, [23] luminescence, [33][34][35] and photocatalysis, [20,[36][37][38] compared with their corresponding imine-linked 2D COF analogs.…”

Section: Introductionmentioning

confidence: 99%

Combination of Knoevenagel Polycondensation and Water‐Assisted Dynamic Michael‐Addition‐Elimination for the Synthesis of Vinylene‐Linked 2D Covalent Organic Frameworks

Liao

Dianat

et al. 2022

Angewandte Chemie

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Vinylene‐linked two‐dimensional conjugated covalent organic frameworks (V‐2D‐COFs), belonging to the class of two‐dimensional conjugated polymers, have attracted increasing attention due to their extended π‐conjugation over the 2D backbones associated with high chemical stability. The Knoevenagel polycondensation has been demonstrated as a robust synthetic method to provide cyano (CN)‐substituted V‐2D‐COFs with unique optoelectronic, magnetic, and redox properties. Despite the successful synthesis, it remains elusive for the relevant polymerization mechanism, which leads to relatively low crystallinity and poor reproducibility. In this work, we demonstrate the novel synthesis of CN‐substituted V‐2D‐COFs via the combination of Knoevenagel polycondensation and water‐assisted dynamic Michael‐addition‐elimination, abbreviated as KMAE polymerization. The existence of C=C bond exchange between two diphenylacrylonitriles (M1 and M6) is firstly confirmed via in situ high‐temperature NMR spectroscopy study of model reactions. Notably, the intermediate M4 synthesized via Michael‐addition can proceed the Michael‐elimination quantitatively, leading to an efficient C=C bond exchange, unambiguously confirming the dynamic nature of Michael‐addition‐elimination. Furthermore, the addition of water can significantly promote the reaction rate of Michael‐addition‐elimination for highly efficient C=C bond exchange within 5 mins. As a result, the KMAE polymerization provides a highly efficient strategy for the synthesis of CN‐substituted V‐2D‐COFs with high crystallinity, as demonstrated by four examples of V‐2D‐COF‐TFPB‐PDAN, V‐2D‐COF‐TFPT‐PDAN, V‐2D‐COF‐TFPB‐BDAN, and V‐2D‐COF‐HATN‐BDAN, based on the simulated and experimental powder X‐ray diffraction (PXRD) patterns as well as N2‐adsorption–desorption measurements. Moreover, high‐resolution transmission electron microscopy (HR‐TEM) analysis shows crystalline domain sizes ranging from 20 to 100 nm for the newly synthesized V‐2D‐COFs.

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“…Recently, considerable attention has been paid to the construction of olefin-based COFs with C=C bond linkages. [37] The C=C bond is more stable and electron delocalization than traditional the imine bond, most olefin-based COFs have showed excellent stability and luminescent property. [38][39][40][41] Thus, the olefin-based COF (named COFÀ PyÀ AN) was synthesized as previous reports [42,43] by using 1,3,6,8-tetrakis (4-formylphenyl) pyrene (TFPPy) and 1,4-phenylenediacetonitrile (PDAN) through the Knoevenagel condensation reaction.…”

Section: Introductionmentioning

confidence: 99%

An Olefin‐based, Fluorescent Covalent Organic Framework for Selective Sensing of Aromatic Amines

Ying-hu

Yang

et al. 2022

Chemistry An Asian Journal

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Owing to various chemical structures and different basicity of amines, a fluorescent probe that could distinguish aromatic and aliphatic amines is highly desirable for practical applications. Herein, an olefin-based, fluorescent COF (COFÀ PyÀ AN) with unique π-electron deficient groups was synthesized, which was a functionalized platform to realize sensing of π electron-rich aromatic amines. COFÀ PyÀ AN displayed fluorescence quenching in the presence of aromatic amines like aniline, with excellent selectivity against a variety of aromatic molecules, and the detection limit of COFÀ PyÀ AN toward aniline was as low as 1.29 μM. More importantly, COFÀ PyÀ AN could realize discriminating between aromatic and aliphatic amines. Furthermore, density functional theory calculations showed that the photoinduced electron transfer mechanism contributes to fluorescence sensing. This is the first example of olefin-based fluorescent COF materials for selective sensing of aromatic amines.

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All sp2 carbon covalent organic frameworks

Cited by 85 publications

References 57 publications

Module‐Patterned Polymerization towards Crystalline 2D sp²‐Carbon Covalent Organic Framework Semiconductors

Module‐Patterned Polymerization towards Crystalline 2D sp²‐Carbon Covalent Organic Framework Semiconductors

Combination of Knoevenagel Polycondensation and Water‐Assisted Dynamic Michael‐Addition‐Elimination for the Synthesis of Vinylene‐Linked 2D Covalent Organic Frameworks

An Olefin‐based, Fluorescent Covalent Organic Framework for Selective Sensing of Aromatic Amines

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All sp2 carbon covalent organic frameworks

Cited by 85 publications

References 57 publications

Module‐Patterned Polymerization towards Crystalline 2D sp2‐Carbon Covalent Organic Framework Semiconductors

Module‐Patterned Polymerization towards Crystalline 2D sp2‐Carbon Covalent Organic Framework Semiconductors

Combination of Knoevenagel Polycondensation and Water‐Assisted Dynamic Michael‐Addition‐Elimination for the Synthesis of Vinylene‐Linked 2D Covalent Organic Frameworks

An Olefin‐based, Fluorescent Covalent Organic Framework for Selective Sensing of Aromatic Amines

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Module‐Patterned Polymerization towards Crystalline 2D sp²‐Carbon Covalent Organic Framework Semiconductors

Module‐Patterned Polymerization towards Crystalline 2D sp²‐Carbon Covalent Organic Framework Semiconductors