Kolmer M, Zuzak R, Steiner A K, Zajac L, Engelund M, Godlewski S, Szymonski M, Amsharov K
Centre for Nanometer-Scale Science and Advanced Materials, NANOSAM, Faculty of Physics, Astronomy and Applied Computer Science, Jagiellonian University, Łojasiewicza 11, 30-348 Kraków, Poland.
Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA.
Science. 2019 Jan 4;363(6422):57-60. doi: 10.1126/science.aav4954.
The rational synthesis of nanographenes and carbon nanoribbons directly on nonmetallic surfaces has been an elusive goal for a long time. We report that activation of the carbon (C)-fluorine (F) bond is a reliable and versatile tool enabling intramolecular aryl-aryl coupling directly on metal oxide surfaces. A challenging multistep transformation enabled by C-F bond activation led to a dominolike coupling that yielded tailored nanographenes directly on the rutile titania surface. Because of efficient regioselective zipping, we obtained the target nanographenes from flexible precursors. Fluorine positions in the precursor structure unambiguously dictated the running of the "zipping program," resulting in the rolling up of oligophenylene chains. The high efficiency of the hydrogen fluoride zipping makes our approach attractive for the rational synthesis of nanographenes and nanoribbons directly on insulating and semiconducting surfaces.
长期以来，直接在非金属表面合理合成纳米石墨烯和碳纳米带一直是一个难以实现的目标。我们报告称，碳（C）-氟（F）键的活化是一种可靠且通用的工具，可实现直接在金属氧化物表面进行分子内芳基-芳基偶联。由C-F键活化实现的具有挑战性的多步转化导致了一种多米诺状偶联，直接在金红石型二氧化钛表面生成了定制的纳米石墨烯。由于高效的区域选择性拉链式反应，我们从柔性前体获得了目标纳米石墨烯。前体结构中的氟位置明确决定了“拉链程序”的运行，导致寡聚苯链卷曲。氟化氢拉链式反应的高效率使我们的方法对于直接在绝缘和半导体表面合理合成纳米石墨烯和纳米带具有吸引力。
