Bonding between π-Conjugated Polycations and Monolayer Graphene: Decisive Role of Anions

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