Chemical reactions that convert sp2 to sp3 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.
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The methods and materials used in this study are available in the Supplementary Information. The authors declare that all data supporting the findings of this study are available within the paper and its Supplementary Information. Correspondence and requests for materials should be addressed to M.Y, A.G., L.K or F. B.
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This work was financially supported by the National Natural Science Foundation of China (grant nos. 21473045, 51772066, 21603086, U1930402), the Engineering and Physical Sciences Research Council (grant nos. EP/L000202, EP/P020194), and the State Key Laboratory of Urban Water Resource and Environment (grant no. 2018DX04). We acknowledge X. Yang (Dalian Institute of Chemical Physics, Chinese Academy of Sciences) for the initial idea of triggering the reaction by ultraviolet irradiation and useful discussion. We also acknowledge the computational support from the Beijing Computational Science Research Center. F.R. acknowledges partial salary support from the Canada Research Chairs programme.
The authors declare no competing interests.
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Yu, M., Chen, C., Liu, Q. et al. Long-range ordered and atomic-scale control of graphene hybridization by photocycloaddition. Nat. Chem. 12, 1035–1041 (2020). https://doi.org/10.1038/s41557-020-0540-2
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