2017/01/29 by Demetrios D. Chronopoulos, Aristides Bakandritsos, Petr Lazar +4 · 4 citations
Chemistry · Engineering · Materials Science · #Fullerene Chemistry and Applications #Graphene research and applications #Molecular Junctions and Nanostructures
paper · pdf · doi:10.1021/acs.chemmater.6b05040
openalex publication_date 2017/01/29 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/04
C ovalent functionalization of graphene significantly broad- ens its application potential via tuning its electronic and surface properties. 1,2Therefore, a wide range of dry and wet chemistry approaches have been developed for graphene functionalization. [3][4]4][5][6][7] Despite recent progress in this field, covalent modification of graphene is still hampered by its low reactivity.Moreover, the reactivity depends on the type of graphene support 8,9 and number of graphene layers. [10][11]][12] Consequently, there is a need for new strategies that permit high yielding graphene functionalization under more controlled conditions.Very recently, fluorographene (FG), a stoichiometric (C 1 F 1 ) and well-established graphene derivative, [13][14][15][16][17][18] has been shown to be susceptible to reductive defluorination 14 and nucleophilic attack. 19These findings suggest that FG may be a useful alternative material to graphene for the preparation of graphene derivatives.This idea is supported by recent achievements in the field employing nucleophilic substitution of fluorine atoms by other groups, such as sulfhydryl, 20 amino, 21-24 alkoxy, 22 dichlorocarbene 25 and urea. 26However, efficient reaction of FG with Grignard reagents to allow high yield alkylation and arylation of graphene has not yet been reported.The Grignard reaction is one of the most well-established methodologies for the formation of C-C bonds in organic chemistry.Grignard reagents bear a nucleophilic carbon atom owing to its bonding to magnesium, and the in situ formed hydrocarbon anion can attack electrophilic carbons, such as the carbons of FG. 19,22 The Grignard reaction has been successfully applied to fluorinated carbon nanotubes, 27 but to date, there is only one report regarding the covalent modification of chlorinated graphene with Grignard reagents. 28Very recently, the same group reported that Grignard reaction on fluorinated epitaxial graphene was not feasible. 29n the present work, we report the first successful covalent modification of FG based on the Grignard reaction, which yielded homogeneous and high-density (5.5-11.2%)functionalization of the graphene surface.Three different types of organometallic reagents, containing alkane (pentyl), alkene (allyl), and aryl (anisolyl or p-methoxyphenyl) moieties, reacted successfully, unlike the reaction with the ethynyl reagent.This behavior was rationalized in terms of the nucleophilicities of the reactive centers, assessed by computational chemistry (Figure 1).The new covalently functionalized graphene derivatives were characterized by complementary techniques: spectroscopic, thermogravimetric and microscopic.In addition, we used density functional theory (DFT) calculations to evaluate