Crystalline Dioxin-Linked Covalent Organic Frameworks from Irreversible Reactions,Journal of the American Chemical Society

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Crystalline Dioxin-Linked Covalent Organic Frameworks from Irreversible Reactions
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-09-24 , DOI: 10.1021/jacs.8b08374
Bing Zhang ₁ , Mufeng Wei ₁ , Haiyan Mao ₂ , Xiaokun Pei ₁ , Sultan A. Alshmimri ₃ , Jeffrey A. Reimer ₂ , Omar M. Yaghi _{1,

3}

Affiliation

Triangular 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and linear tetrafluorophthalonitrile (TFPN) or 2,3,5,6-tetrafluoro-4-pyridinecarbonitrile (TFPC) were linked by 1,4-dioxin linkages to form crystalline 2D covalent organic frameworks, termed COF-316 and -318. Unlike the condensation reactions commonly used to crystallize the great majority of COFs, the reactions used in this report are based on nucleophilic aromatic substitution reactions (SNAr) that are considered irreversible. Our studies show that the reactivity of TFPN and TFPC with HHTP is enhanced by the nitrile substituents leading to facile reactions of planar building units to yield the present 1,4-dioxin linked COFs. Because these reactions are irreversible, the resultant frameworks have high chemical stability in both acid and base. This has led to postsynthetic modifications of COF-316 by reactions necessitating extreme conditions to covalently install functionalities not otherwise accessible. We also report the permanent porosity of these COFs.

中文翻译：

来自不可逆反应的结晶二恶英连接的共价有机骨架

三角形 2,3,6,7,10,11-六羟基苯并苯 (HHTP) 和线性四氟邻苯二甲腈 (TFPN) 或 2,3,5,6-四氟-4-吡啶甲腈 (TFPC) 通过 1,4-二恶英键连接到形成结晶二维共价有机骨架，称为 COF-316 和 -318。与通常用于结晶绝大多数 COF 的缩合反应不同，本报告中使用的反应基于被认为是不可逆的亲核芳香取代反应 (SNAr)。我们的研究表明，腈取代基增强了 TFPN 和 TFPC 与 HHTP 的反应性，从而导致平面构建单元的轻松反应，从而产生了当前的 1,4-二恶英连接的 COF。由于这些反应是不可逆的，因此所得骨架在酸和碱中均具有高化学稳定性。这导致 COF-316 的合成后修饰通过需要极端条件的反应来共价安装其他方式无法获得的功能。我们还报告了这些 COF 的永久孔隙率。

更新日期：2018-09-24

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