Abstract
A novel type of a graphene‐porphyrin hybrid with a direct covalent linker between graphene and a nickel(II) tetraphenylporphyrin unit has successfully been synthesized by the reductive exfoliation/functionalization of potassium intercalated graphite as starting material. Moreover, we directly compared the reactivity of two structurally different porphyrin derivatives, namely, meso‐NiTPP‐N2+, with the diazonium group in 4′‐position of a peripheral phenyl ring and a novel β‐NiTPP‐N2+ diazonium cation, where the diazonium group is directly attached to the β‐pyrrolic position of the 18 π electron core. Due to sterical restraints, this intermediately generated porphyrin radical cannot attack the extended π surface of graphene and only a functionalization of present dangling bonds at the flake edges may be obtained in this case. All reaction products have been analyzed in detail be means of Raman and UV/Vis spectroscopy as well as thermogravimetric analysis.
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