▎ 摘　　要

Despite holding unique electronic, optical, mechan-ical, and thermal properties, some inherent characteristics ofgraphene restrict its widespread use in technological applicationssuch as digital electronics. The introduction of ordered organicadlayers on top of graphene has been identified as a potentialapproach to tune its electronic band structure via quantumconfinement effects caused by molecular-scale ordering within theadsorbate layers. To this end, the redox-dependent self-assembledmolecular architectures of dibenzyl viologen (DBV) on graphiticsurfaces including graphene are investigated under electrochemicalcontrol. Molecular-resolution electrochemical scanning tunnelingmicroscopy results reveal three architectures, namely, the mobile,dimer, and stacking phases, corresponding to different DBV redox states, that is, DBV2+, DBV center dot+, and DBV0, respectively, formed andstabilized on both highly oriented pyrolytic graphite and chemical vapor deposition graphene on a copper foil. The phase transitionis fully controlled by the applied electrode potential. The patterned functionalization of graphitic surfaces via laterally confined self-assembly of DBV molecules was demonstrated. Thesefindings may help pave the way to functionalize graphene and other two-dimensional materials in both global and patterned manners by means of viologen-based self-assemblies.