Inorganic Chemistry, Technische Universität Dresden, Bergstraße 66, 01062, Dresden, Germany.
Organische Chemie, TU Dresden, Bergstraße 66, 01062, Dresden, Germany.
Angew Chem Int Ed Engl. 2017 Jun 6;56(24):6859-6863. doi: 10.1002/anie.201702303. Epub 2017 May 10.
This study elucidates an innovative mechanochemical approach applying Friedel-Crafts alkylation to synthesize porous covalent triazine frameworks (CTFs). Herein, we pursue a counterintuitive approach by utilizing a rather destructive method to synthesize well-defined materials with intrinsic porosity. Investigating a model system including carbazole as monomer and cyanuric chloride as triazine node, ball milling is shown to successfully yield porous polymers almost quantitatively. We verified the successful structure formation by an in-depth investigation applying XPS, solid-state NMR and FT-IR spectroscopy. An in situ study of pressure and temperature developments inside the milling chamber in combination with two-dimensional liquid-state NMR spectroscopy reveals insights into the polymerization mechanism. The versatility of this mechanochemical approach is showcased by application of other monomers with different size and geometry.
本研究阐明了一种创新的机械化学方法，应用傅-克烷基化反应合成多孔共价三嗪框架（CTFs）。在此，我们采用一种反直觉的方法，利用相当具有破坏性的方法来合成具有固有孔隙率的明确定义的材料。通过研究包括咔唑作为单体和三聚氰胺作为三嗪节点的模型体系，球磨被证明可以几乎定量地成功合成多孔聚合物。我们通过 XPS、固态 NMR 和傅里叶变换红外光谱的深入研究验证了成功的结构形成。在研磨室内压力和温度发展的原位研究与二维液体 NMR 光谱学相结合，揭示了聚合机制的深入了解。通过应用具有不同尺寸和几何形状的其他单体，展示了这种机械化学方法的多功能性。
