Kondo resonances in heterostructures formed by magnetic molecules on a metal require free host electrons to interact with the molecular spin and create delicate many-body states. Unlike graphene, semiconducting graphene nanoribbons do not have free electrons due to their large bandgaps, and thus they should electronically decouple molecules from the metal substrate. Here, we observe unusually well-defined Kondo resonances in magnetic molecules separated from a gold surface by graphene nanoribbons in vertically stacked heterostructures. Surprisingly, the strengths of Kondo resonances for the molecules on graphene nanoribbons appear nearly identical to those directly adsorbed on the top, bridge and threefold hollow sites of Au(111). This unexpectedly strong spin-coupling effect is further confirmed by density functional calculations that reveal no spin–electron interactions at this molecule-gold substrate separation if the graphene nanoribbons are absent. Our findings suggest graphene nanoribbons mediate effective spin coupling, opening a way for potential applications in spintronics.
Complexes containing rare-earth ions attract great attention for their technological applications ranging from spintronic devices to quantum information science. While charged rare-earth coordination complexes are ubiquitous in solution, they are challenging to form on materials surfaces that would allow investigations for potential solid-state applications. Here we report formation and atomically precise manipulation of rare-earth complexes on a gold surface. Although they are composed of multiple units held together by electrostatic interactions, the entire complex rotates as a single unit when electrical energy is supplied from a scanning tunneling microscope tip. Despite the hexagonal symmetry of the gold surface, a counterion at the side of the complex guides precise three-fold rotations and 100% control of their rotational directions is achieved using a negative electric field from the scanning probe tip. This work demonstrates that counterions can be used to control dynamics of rare-earth complexes on materials surfaces for quantum and nanomechanical applications.
Charge density waves have been intensely studied in inorganic materials such as transition metal dichalcogenides; however their counterpart in organic materials has yet to be explored in detail. Here we report the finding of robust two-dimensional charge density waves in molecular layers formed by α-(BEDT-TTF)2–I3 on a Ag(111) surface. Low-temperature scanning tunneling microscopy images of a multilayer thick α-(BEDT-TTF)2–I3 on a Ag(111) substrate reveal the coexistence of 5a 0 × 5a 0 and R9° charge density wave patterns commensurate with the underlying molecular lattice at 80 K. Both charge density wave patterns remain in nanosize molecular islands with just a single constituent molecular-layer thickness at 80 and 5 K. Local tunneling spectroscopy measurements reveal the variation of the gap from 244 to 288 meV between the maximum and minimum charge density wave locations. Density functional theory calculations further confirm a vertical positioning of BEDT-TTF molecules in the molecular layer. While the observed charge density wave patterns are stable for the defect sites, they can be reversibly switched for one molecular lattice site by means of inelastic tunneling electron energy transfer with the electron energies exceeding 400 meV using a scanning tunneling microscope manipulation scheme.
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