Phenylenediamine-Linked, Folded Nanographene Dimers: Access to Structure-Dependent Redox Capability

Abstract

Polycyclic aromatic hydrocarbons (PAHs) with open-shell or redox characteristics are highly desirable due to their intriguing electronic properties and potential applications. Here, we demonstrate a series of phenylenediamine-linked nanographenes (NGs) 1–3 by connecting two aza-hexa-peri-hexabenzocoronene (HBC) units to p-phenylene, p,p’-biphenylene, and p,p”-terphenylene, respectively, and unveil their 3D conformations, electronic structures, and redox properties. As proved by X-ray crystallographic analysis and quantum chemical calculation, 1–3 adopted anti-folded, Z-shaped 3D structures with rotatable single bonds. The structure-dependent redox capabilities were disclosed. For 1, a stable monoradical cation was generated by one-electron oxidation as the terminal product. X-ray crystallographic analysis revealed an unprecedented syn-folded structure of monoradical 1⁺. However, 2 and 3 were demonstrated as redox-active molecules from neutral to dication that each oxidative state can be precisely controlled by chemical oxidation/reduction.