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Covalent functionalization by cycloaddition reactions of pristine, defect-free graphene

Based on a low temperature scanning tunneling microscopy study, we present a direct visualization of a cycloaddition reaction performed for some specific fluorinated maleimide molecules deposited on graphene. These studies showed that the cycloaddition reactions can be carried out on the basal plane of graphene, even when there are no pre-existing defects. In the course of covalently grafting the molecules to graphene, the sp2 conjugation of carbon atoms was broken and local sp3 bonds were created. The grafted molecules perturbed the graphene lattice, generating a standing-wave pattern with an anisotropy which was attributed to a (1,2) cycloaddition, as revealed by T-matrix approximation calculations. DFT calculations showed that while both (1,4) and (1,2) cycloaddition were possible on free standing graphene, only the (1,2) cycloaddition could be obtained for graphene on SiC(0001). Globally averaging spectroscopic techniques, XPS and ARPES, were used to determine the modification in the elemental composition of the samples induced by the reaction, indicating an opening of an electronic gap in graphene.