title: Sulfur-annulated hexa-peri-hexabenzocoronene decorated with phenylthio groups at the periphery.
abstract: The chemical nature of the edge periphery essentially determines the physical properties of graphene. As a molecular-level model system, large polycyclic aromatic hydrocarbons, that is, so-called nanographenes, can be chemically modified through either edge functionalization or doping with heteroatoms. Although the synthetic methods for edge substitution are well-developed, incorporation with heteroatoms by the bay annulation of large PAHs remains an enormous challenge. In this study, we present a feasible peripheral sulfur annulation of hexa-peri-hexabenzocoronene (HBC) by thiolation of perchlorinated HBC. The tri-sulfur-annulated HBC and di-sulfur-annulated HBC decorated with phenylthio groups were obtained and characterized by X-ray diffraction, revealing their distinct sulfur-annulated peripheral structure. Associated with theoretical calculations, we propose that the regioselective sulfur annulation results from the minimization of strain in the aromatic backbone. We further demonstrate the structure-correlated property modulation by sulfur annulation, manifested by a decrease in band gap and tunable redox activity.
authors.affiliation: Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz (Germany); State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, 361005, Xiamen (China).
authors.forename: Yuan-Zhi
authors.initials: YZ
authors.lastname: Tan
authors.forename: Silvio
authors.initials: S
authors.lastname: Osella
authors.forename: Yi
authors.initials: Y
authors.lastname: Liu
authors.forename: Bo
authors.initials: B
authors.lastname: Yang
authors.forename: David
authors.initials: D
authors.lastname: Beljonne
authors.forename: Xinliang
authors.initials: X
authors.lastname: Feng
authors.forename: Klaus
authors.initials: K
authors.lastname: Müllen
keywords: annulation; functionalization; nanographene; sulfur; thiolation