Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
J Am Chem Soc. 2020 Oct 21;142(42):17876-17880. doi: 10.1021/jacs.0c05965. Epub 2020 Oct 12.
The design and synthesis of molecular systems able to carry out movements resembling macroscopic objects is an exciting and challenging endeavor. Molecules that can walk covalently on a track have been demonstrated, and we now report how aryl groups that can migrate over a graphene surface. Specifically, we describe a system comprised of covalently functionalized aryl groups on graphene that undergo continuous aryl shifts. The dynamic aryl shift allows the aryl groups on graphene to effectively migrate step-by-step wherein each step involves reversible bond breaking and making that is initiated by a combination of an activated arene and p-doping of the graphene surface. Raman spectroscopic mapping of the distribution of the covalent attachment revealed that activated 4-methoxyphenyl groups migrate several microns from regions of high functionalization to regions with no prior functionalization.
设计和合成能够进行类似于宏观物体运动的分子系统是一项令人兴奋和具有挑战性的工作。已经证明了能够在轨道上进行共价行走的分子，我们现在报告如何使芳基基团能够在石墨烯表面上迁移。具体来说，我们描述了一个由共价功能化的芳基基团组成的系统，该系统在石墨烯上经历连续的芳基移位。动态芳基移位使石墨烯上的芳基基团能够有效地逐步迁移，其中每个步骤都涉及可逆的键断裂和形成，这是由活化的芳烃和石墨烯表面的 p 掺杂共同引发的。对共价附着分布的拉曼光谱映射表明，活化的 4-甲氧基苯基基团从高功能化区域迁移到没有先前功能化的区域几微米。
