Gating Single Molecules with Counterions.

We report atomic-scale gating and visualization of local charge distribution within individual rare-earth-based molecular complexes on a metallic surface. The complexes are formed by a positively charged lanthanum ion coordinated to a (pcam) molecule and a negatively charged counterion trapped underneath via electrostatic interactions on a Au(111) surface. Local gating is performed by adding an additional negatively charged counterion to one side of the complex, which results in the redistribution of charges within the complex and a positive shift of the frontier orbitals. This is caused by the internal Stark effect induced by the added counterion. This effect is directly captured using tunneling spectroscopy and spectroscopic mapping at 5 K substrate temperature. The polarizability of the complex is corroborated by density functional theory and analytical calculations based on experimental findings. Furthermore, the influence of charge polarization on nearby complexes is investigated in a cluster purposely assembled using three complexes, which reveals maintaining the charge states as in single complexes. These findings will enable the design of robust charged rare-earth complexes to be tailored for potential solid-state applications.