Yu Miao, Chen Chong, Liu Qi, Mattioli Cristina, Sang Hongqian, Shi Guoqiang, Huang Wujun, Shen Kongchao, Li Zhuo, Ding Pengcheng, Guan Pengfei, Wang Shaoshan, Sun Ye, Hu Jinping, Gourdon André, Kantorovich Lev, Besenbacher Flemming, Chen Mingshu, Song Fei, Rosei Federico
State Key Laboratory of Urban Water Resource and Environment, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, China.
Beijing Computational Science Research Center, Beijing, China.
Nat Chem. 2020 Nov;12(11):1035-1041. doi: 10.1038/s41557-020-0540-2. Epub 2020 Oct 19.
Chemical reactions that convert sp to sp hybridization have been demonstrated to be a fascinating yet challenging route to functionalize graphene. So far it has not been possible to precisely control the reaction sites nor their lateral order at the atomic/molecular scale. The application prospects have been limited for reactions that require long soaking, heating, electric pulses or probe-tip press. Here we demonstrate a spatially selective photocycloaddition reaction of a two-dimensional molecular network with defect-free basal plane of single-layer graphene. Directly visualized at the submolecular level, the cycloaddition is triggered by ultraviolet irradiation in ultrahigh vacuum, requiring no aid of the graphene Moiré pattern. The reaction involves both [2+2] and [2+4] cycloadditions, with the reaction sites aligned into a two-dimensional extended and well-ordered array, inducing a bandgap for the reacted graphene layer. This work provides a solid base for designing and engineering graphene-based optoelectronic and microelectronic devices.
将sp杂化转变为sp² 杂化的化学反应已被证明是一条使石墨烯功能化的迷人但具有挑战性的途径。到目前为止，还无法在原子/分子尺度上精确控制反应位点及其横向排列顺序。对于需要长时间浸泡、加热、电脉冲或探针尖端按压的反应，其应用前景一直有限。在此，我们展示了二维分子网络与单层石墨烯无缺陷基面的空间选择性光环加成反应。在亚分子水平上直接观察到，该光环加成反应是在超高真空中由紫外线照射引发的，无需石墨烯莫尔图案的辅助。该反应涉及[2+2]和[2+4]光环加成，反应位点排列成二维扩展且有序的阵列，为反应后的石墨烯层诱导出带隙。这项工作为设计和制造基于石墨烯的光电器件和微电子器件提供了坚实基础。
