Controllable synthesis of graphene derivatives with defined composition and properties represents the holy grail of graphene chemistry, especially in view of the low reactivity of graphene. Recent progress in fluorographene (FG) chemistry has opened up new routes for synthesizing a plethora of graphene derivatives with widely applicable properties, but they are often difficult to control. We explored nucleophilic substitution on FG combining density functional theory calculations with experiments to achieve accurate control over the functionalization process. In-depth analysis revealed the complexity of the reaction and identified basic rules for controlling the 2D chemistry. Their application, that is, choice of solvent and reaction time, enabled facile control over the reaction of FG with N-octylamine to form graphene derivatives with tailored content of the alkylamine functional group (2.5-7.5% N atomic content) and F atoms (31.5-3.5% F atomic content). This work substantially extends prospects for the controlled covalent functionalization of graphene.

中文翻译：

---

2D化学：石墨烯衍生化的化学控制。

具有确定的组成和性质的可控制的石墨烯衍生物的合成代表了石墨烯化学的圣杯，特别是考虑到石墨烯的低反应性。氟代石墨烯（FG）化学的最新进展为合成大量具有广泛应用特性的石墨烯衍生物开辟了新途径，但它们通常很难控制。我们在结合密度泛函理论计算与实验的FG上探索了亲核取代反应，以实现对官能化过程的精确控制。深入分析揭示了反应的复杂性，并确定了控制2D化学反应的基本规则。它们的应用，即溶剂和反应时间的选择，可以轻松控制FG与N-辛胺形成的石墨烯衍生物，其中石墨烯衍生物的烷基胺官能团含量（N原子含量为2.5-7.5％）和F原子的含量经过调整（F原子含量为31.5-3.5％）。这项工作大大扩展了石墨烯可控共价官能化的前景。