Thermally/hydrolytically stable covalent organic frameworks from a rigid macrocyclic host

Song, Jingru; Sun, Junliang; Liu, Jun‐Min; Huang, Zhi‐Tang; Zheng, Qiang

doi:10.1039/c3cc47652a

Cited by 68 publications

(34 citation statements)

References 47 publications

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“…31 The maximum hydrogen uptake for these COFs was 1.3 wt% at 1.1 bar and 1.23 wt% at 1 bar which is similar to that observed for ILCOF-1. 31 The maximum hydrogen uptake for these COFs was 1.3 wt% at 1.1 bar and 1.23 wt% at 1 bar which is similar to that observed for ILCOF-1.…”

Section: Cof Derivatives For Gas Storage Applicationssupporting

confidence: 77%

Covalent organic frameworks based on Schiff-base chemistry: synthesis, properties and potential applications

2016

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Covalent organic-frameworks (COFs) are an emerging class of porous and ordered materials formed by condensation reactions of organic molecules. Recently, the Schiff-base chemistry or dynamic imine-chemistry has been widely explored for the synthesis of COFs. The main reason for this new tendency is based on their high chemical stability, porosity and crystallinity in comparison to previously reported COFs. This critical review article summarizes the current state-of-the-art on the design principles and synthetic strategies toward COFs based on Schiff-base chemistry, collects and rationalizes their physicochemical properties, as well as aims to provide perspectives of potential applications which are at the forefront of research in materials science.

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Section: Cof Derivatives For Gas Storage Applicationssupporting

confidence: 77%

Covalent organic frameworks based on Schiff-base chemistry: synthesis, properties and potential applications

2016

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“…[10][11][12][13][14][15][16] The methodologies involved in the fabrication of COFs usually need harsh experimental conditions such as reaction in a sealed pyrex tube, inert atmosphere, and long time. [17][18][19][20] In addition, most synthesized COFs require special care in regard to their moisture instability. 21 Likewise, the COFs obtained from previous methods are usually irregular shaped.…”

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confidence: 99%

Facile room-temperature solution-phase synthesis of a spherical covalent organic framework for high-resolution chromatographic separation

et al. 2015

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A simple and facile room-temperature solution-phase synthesis was developed to fabricate a spherical covalent organic framework with large surface area, good solvent stability and high thermostability for high-resolution chromatographic separation of diverse important industrial analytes including alkanes, cyclohexane and benzene, α-pinene and β-pinene, and alcohols with high column efficiency and good precision.

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“…如图 1 扫描电子显微镜(SEM)和光学显微镜图像显示, CD-MOF(γ-环糊精 MOF)为表面光滑, 大小为 50 µm 的立方晶体; CL-CD-MOF(Cross-linked γ-环糊精 MOF)仍为 50 µm 的立方晶体, 但与 CD-MOF 相比较, 表面相对粗糙, 从而证实了对苯二硼酸与 CD-MOF 发生了交联反应. 值得注意的是, 由于 γ-CD (γ-环糊精)的多碳链结构和多重的空间阻碍, 并且外层硼酸酯与 NH 3 •H 2 O 之间形成配位键, 导致形成的硼酸酯键在水的存在下能够稳定 [21,22] . CD-MOF 晶体完全溶解在水里, 而 CL-CD-MOF 只是部分溶解而形成 Z-cage.…”

Section: 结果与讨论unclassified

Fabrication of Porous Covalent Organic Cages Using Cyclodextrin Metal-Organic Frameworks as Template

Zhang¹,

Liu²,

Xie³

2015

Acta Chim. Sinica

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Up to now, transformation from metal-organic frameworks (MOFs) to covalent-organic-framework cages (COF-Cages) has never been reported. In this report, we demonstrated an organic cage crystal by transformation from a cyclodextrin MOF, via boronate ester formation reaction of the hydroxy groups of γ-CD inside the MOF, followed by removing of the potassium ions. First, CD-MOF was prepared by reacting γ-CD with potassium hydroxide in aqueous solution, followed by vapor diffusion of methanol into the solution according to a previously reported method. The freshly prepared CD-MOF was first washed with ethanol three times to remove the unreacted reactants, and then added to an ethanol saturated solution of benzene-1,4-diboronic acid (BDBA) in a screw top vial, and kept it at 65 ℃ for three days. Finally, the covalent cross-linked CD-MOF (CL-CD-MOF) was obtained by forming boronic esters between the uncoordinated C(2) and C(3) hydroxy groups of contiguous γ-CD sides in the CD-MOF pores and two boronic acid groups of BDBA. Structure and physical properties of Z-Cages were fully characterized by thermogravimetric analysis (TGA), infrared spectroscopy (IR), powder X-ray diffraction (PXRD), solid-state 13 C and 11 B cross polarization/magic angle spining nuclear magnetic resonance (CP/MAS/NMR) spectroscopy and nitrogen adsorption. The obtained zeolite-type organic cage (Z-cage) displayed a targeted sodalite-type crystalline structure and permanent porosity with the surface area of 862 m 2 •g-1. A control experiment, the cross-linked polymers (CL-polymer) formed by coupling of γ-CD and BDBA was done by solvothermal method. The CL-polymer was synthesized by the heating of a 4∶1 stoichiometric mixture of BDBA and γ-CD at 90 ℃ for three days in dimethylformamide (DMF). PXRD pattern shows the CL-polymer are crystalline, but totally different with Z-cage. This transformation from crystalline inorganic-organic hybrid framework of MOF to crystalline organic framework provides an opportunity for crystal-to-crystal in porous crystalline materials. Keywords γ-CD; metal-organic frameworks; organic cage; cross-linked polymers; templated synthesis 1 引言多孔固体有机物, 如共价有机骨架(covalent organic frameworks)和多孔有机笼(porous organic cages), 由于它们在气体存储、分子分离、催化等方面具有广泛的应用, 成为许多科研人员研究的重点 [1～3]. 结晶性有机笼是由动态、可逆的化学键, 如希夫碱或硼酸酯的自组装

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Thermally/hydrolytically stable covalent organic frameworks from a rigid macrocyclic host

Cited by 68 publications

References 47 publications

Covalent organic frameworks based on Schiff-base chemistry: synthesis, properties and potential applications

Covalent organic frameworks based on Schiff-base chemistry: synthesis, properties and potential applications

Facile room-temperature solution-phase synthesis of a spherical covalent organic framework for high-resolution chromatographic separation

Fabrication of Porous Covalent Organic Cages Using Cyclodextrin Metal-Organic Frameworks as Template

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