Screening the 4f-electron spin of TbPc₂ single-molecule magnets on metal substrates by ligand channeling

Bis(phthalocyaninato)lanthanide (LnPc₂) double-decker-based devices have recently attracted a great deal of interest for data encoding purposes. Although the 4f-electrons of lanthanide ions play a key role in the experimental methodology, their localized character, deeper in energy compared to the 3d electrons of transition metals, hampers a detailed investigation. Here, our approach consists of the follow-up of the entanglement process with other molecules and with the substrate electrons by means of space-resolved detection of the Kondo resonance by scanning tunneling spectroscopy (STS), using different substrates (from weak to strong interaction). It is found that TbPc₂ molecules firstly interact with their environment by means of the π-radicals of the ligand. The radical spin of TbPc₂ can be identified by STS on a weakly interacting substrate such as Au(111). In the case of a Ag(111) substrate, we are able to analyze the effect of an electron transfer on the molecule (pairing-up of the radical spin) and the subsequent quenching of the Kondo resonance. Finally, on a strongly interacting substrate such as Cu(111), a significant rearrangement of electrons takes place and the Kondo screening of the 4f electrons of the Tb ion of TbPc₂ is observed. By comparative STS measurements on YPc₂, that has empty 4d and 4f shells, we prove that the Kondo resonance measured in the center of the TbPc₂ molecule indeed stems from the 4f-electrons. At the same time, we provide evidence for the hybridization of the 4f states with the π electron.