p-Doping of graphene in hybrid materials with 3,10-diazapicenium dications

N,N'-Didodecyl-substituted 3,10-diazapicenium salts featuring bromide and hexafluorophosphate counterions have been designed as novel dopants to realize individualized graphene sheets in a series of cutting edge experiments and to intrinsically stabilize them via p-doping. Importantly, electrochemical studies revealed two consecutive irreversible one-electron reductions of the N,N'-didodecyl-substituted 3,10-diazapicenium salts to yield the corresponding radical cation and neutral quinoidal species. Formation of both species was accompanied by characteristic changes in the absorption spectra. The 3,10-diazapicenium bromide was found to be a potent dopant to produce hybrid materials with exfoliated graphene. Microscopy based on AFM and TEM imaging and spectroscopy based on Raman probing corroborated that, upon drying, the hybrid material consists of few layer (5-8 layers) turbostratic graphene sheets that are p-doped. Our findings identify the newly synthesized N,N'-dialkylated 3,10-diazapicenium salts as highly promising candidates for the fabrication of functional graphene materials with tailored properties.