Department of Chemistry, University of California-Berkeley; Kavli Energy Nanoscience Institute at UC Berkeley; Berkeley Global Science Institute; and Materials Sciences Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , United States.
UC Berkeley-KACST Joint Center of Excellence for Nanomaterials for Clean Energy Applications , King Abdulaziz City for Science and Technology , Riyadh 11442 , Saudi Arabia.
J Am Chem Soc. 2020 Feb 12;142(6):2771-2776. doi: 10.1021/jacs.9b13971. Epub 2020 Feb 3.
The design and synthesis of 2D and 3D crystalline covalent organic frameworks (COFs) from macromolecular and even infinite building units is largely undeveloped. Here, we report a strategy to link molecules and 1D ribbons into 2D cystalline frameworks. Triangular, tris(4-aminophenyl)amine (TAA), and square, 1,3,6,8-tetrakis(-formylphenyl)pyrene (TFPPy), organic building units are joined substoichiometrically by imine linkages to produce 1D ribbons, termed COF-76, bearing free amines, which are then used to link the ribbons into 2D frameworks COF-77 and COF-78. In addition to this stepwise approach, we also demonstrate an synthesis of these COFs. We believe our ability to link infinite building blocks, such as the ribbons of COF-76, into higher dimensionality COFs, paves the way to covalent frameworks composed of hierachical chemical structures.
将大分子甚至无限的构筑单元设计并合成为二维和三维结晶共价有机骨架（COFs）的研究还未得到充分的发展。在此，我们报告了一种将分子和一维带状物连接成二维结晶骨架的策略。我们采用亚化学计量比的方式将三角形的三（4-氨基苯基）胺（TAA）和正方形的 1,3,6,8-四（-醛基苯基）芘（TFPPy）这两种有机构筑单元通过亚胺键连接起来，得到了带有游离氨基的一维带状物 COF-76，然后再利用这些氨基将带状物连接成二维框架 COF-77 和 COF-78。除了这种逐步的方法，我们还展示了这些 COFs 的合成。我们相信，我们将无限构筑单元（如 COF-76 的带状物）连接成更高维 COFs 的能力为构建由层次化化学结构组成的共价骨架铺平了道路。
