Thiol-tethered RuII terpyridine complexes were synthesized for a voltage-driven molecular switch
and used to understand the switch-on mechanism of the molecular switches of single metal complexes in
the solid-state molecular junction in a vacuum. Molecularly resolved scanning tunneling microscopy (STM)
images revealed well-defined single RuII complexes isolated in the highly ordered dielectric monolayer.
When a negative sample-bias was applied, the threshold voltage to the high conductance state in the
molecular junctions of the RuII complex was consistent with the electronic energy gap between the Fermi
level of the gold substrate and the lowest ligand-centered redox state of the metal complex molecule. As
an active redox center leading to conductance switching in the molecule, the lowest ligand-centered redox
state of RuII complexes was suggested to trap an electron injected from the gold substrate. Our suggestions
for a single-molecule switch-on mechanism in the solid state can provide guidance in a design that improves
the charge-trapping efficiency of the ligands with different metal substrates