Functionalization and precise modulation of the electronic properties of graphene are key processes in the development of new applications of this promising material. This study examines the potential of using organic polycations as p-dopants and/or anchoring motifs for non-covalent functionalization. A library of hybrid materials was prepared through wet-chemical non-covalent functionalization. Both chemical vapor deposition graphene and reduced graphene oxide were functionalized with a series of neutral and polycationic benzimidazole-based systems. We report on how both the number of anions and the size, shape, and magnitude of the positive charge of the benzimidazole-based systems cooperatively affect the redox properties as well as the affinity for and the nature of bonding to graphene. The redox properties of the benzimidazole-based systems were studied by cyclic voltammetry. The functionalized graphene materials were characterized by Raman spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry. Density functional theory calculations were performed to make contact between the experimental results obtained for molecular samples and hybrid materials. No universal dependence of the binding affinity on a single parameter, such as the amount of positive charge or the size of the system, was found. Instead, the cooperative effect of the three-dimensional structure of the benzimidazole-based systems and the number of anions was found to play a pivotal role. Together, these parameters determine the degree of partial electron sharing and magnitude of dispersion forces involved in the binding of members of this family of benzimidazole-based systems to graphene.
