Faculty of Chemistry, Warsaw University of Technology , Noakowskiego 3, 00-664 Warszawa, Poland.
Faculty of Chemistry, University of Wrocław , F. Joliot-Curie 14, 50-383 Wrocław, Poland.
ACS Appl Mater Interfaces. 2017 Sep 13;9(36):31129-31141. doi: 10.1021/acsami.7b09061. Epub 2017 Aug 31.
The conversion of 2,4,6-tris(4'-bromophenyl)-1,3,5-triazine to the respective triboronic acid was successfully accomplished by a simple triple Br/Li exchange followed by boronation. Further dehydrative condensation reactions with 2,3,6,7,10,11-hexahydroxytriphenylene or 2,3,6,7-tetrahydroxy-9,10-dilalkylanthracenes (R = Me, Et) resulted in materials featuring good porosity and sorption properties with the nitrogen uptake exceeding 500 cm/g (STP) and S up to 1267 m/g (T = 77.2 K). In addition, simple dehydration of this compound was employed for the preparation of a hybrid 2D COF composed of triazine, boroxine, and benzene rings. The formation of materials was confirmed by the IR analysis and NMR studies on water-decomposed samples. All obtained COFs exhibit high thermal stability with decomposition temperatures in the range of 400-600 °C. They also show quite different morphology ranging from regular 0.5-4 μm spherical and ellipsoidal clusters to 5-12 μm bent rodlike particles. The PXRD studies supported by periodic DFT modeling in Crystal09 package revealed the formation of crystalline 2D honeycomb-type lattices with eclipsed stacking models. In addition, the differences between boroxine-triazine material and related COF-1 and CTF-1 structures were investigated by comparing layer interaction energies, work function values as well as atomic charges and electrostatic potential maps plotted on the electron density surfaces. It demonstrates that the interactions between layers are enhanced by the stacking of triazine and boroxine rings. Finally, we have investigated the upper limit to space accessible volume using a procrystal electron density approach.
将 2,4,6-三(4'-溴苯基)-1,3,5-三嗪成功转化为相应的三硼酸，通过简单的三重 Br/Li 交换和硼化反应完成。进一步与 2,3,6,7,10,11-六羟基三亚苯或 2,3,6,7-四羟基-9,10-二烷基蒽（R = Me，Et）进行脱水缩合反应，得到具有良好孔隙率和吸附性能的材料，氮气吸附量超过 500 cm/g（STP），比表面积高达 1267 m/g（T = 77.2 K）。此外，该化合物的简单脱水反应用于制备由三嗪、硼氧环和苯环组成的混合二维 COF。通过对水分解样品的红外分析和 NMR 研究证实了材料的形成。所有获得的 COF 都具有高热稳定性，分解温度在 400-600°C 范围内。它们还表现出非常不同的形态，从规则的 0.5-4 μm 球形和椭圆形簇到 5-12 μm 的弯曲棒状颗粒。晶胞周期密度泛函理论模型支持的粉末 X 射线衍射研究表明，形成了具有重叠堆积模型的结晶二维蜂窝型晶格。此外，通过比较层间相互作用能、功函数值以及绘制在电子密度表面上的原子电荷和静电势图，研究了硼氧环-三嗪材料与相关 COF-1 和 CTF-1 结构之间的差异。结果表明，三嗪和硼氧环的堆积增强了层间的相互作用。最后，我们使用准晶电子密度方法研究了可及体积的上限。
