Photo-triggered and double functionalization of graphene without use of aggressive photo-generated radicals is a challenging task in two-dimensional chemistry. This was here-in achieved by unravelling the bimodal role of fluorine atoms in fluorographene chemistry: (i) they rendered graphene's double bonds susceptible to reaction with a photo-activated diene and (ii) allowed nucleophilic substitution on F-bonded carbons. Theoretical calculations indicated that the presence of F atoms in the vicinity of sp 2 carbon domains significantly increased bond polarization, turning the otherwise unfeasible on pristine graphene photo-cycloaddition into a very efficient functionalization strategy. Following this strategy, we prepared new graphene derivatives densely and homogeneously covered by functional groups. Furthermore, photo-induced cycloaddition following amine nucleophilic substitution on fluorographene enabled preparation of a bis-functionalized graphene derivative. The reported procedure paves the way toward unexplored graphene derivatives not attainable through known graphene chemistries, which can be utilized in many applications such as dual read-out sensors, drug delivery systems, catalysis, and energy storage.
Barès, H., Bakandritsos, A., Medveď, M., Ugolotti, J., Jakubec, P., Tomanec, O., … Otyepka, M. (2019). Bimodal role of fluorine atoms in fluorographene chemistry opens a simple way toward double functionalization of graphene. Carbon, 145, 251–258. https://doi.org/10.1016/j.carbon.2019.01.059