Kondo Effect of Co-Porphyrin: Remarkable Sensitivity to Adsorption Sites and Orientations.

We investigated the Kondo effect of cobalt(II)-5-15-bis(4'-bromophenyl)-10,20-bis(4'-iodophenyl)porphyrin (CoTPPBr2I2) molecules on Au(111) with low-temperature scanning tunneling microscopy under ultrahigh vacuum conditions. The molecules exhibit four adsorption configurations at the top and bridge sites of the surface with different molecular orientations. The Kondo resonance shows extraordinary sensitivity to the adsorption configuration. By switching the molecule between different configurations, the Kondo temperature is varied over a wide range from ≈8 up to ≈250 K. Density functional theory calculations reveal that changes of the adsorption configuration lead to distinct variations of the hybridization between the molecule and the surface. Furthermore, we show that surface reconstruction plays a significant role for the molecular Kondo effect.

Tilted Spins in Chains of Molecular Switches on Pb(100).

A complex based on a Ni(II) porphyrin exhibiting spin crossover on Ag(111) is studied on Pb(100) by scanning tunneling microscopy at 0.3 K. Strong molecular interactions between the phenyl and pentafluorophenyl moieties lead to the formation of molecular chains and cause a faceting of the substrate surface. The chains are located along double and multiple substrate steps that deviate from high-symmetry directions. Tunneling spectroscopy reveals spin-flip excitations of an S = 1 system. Measurements in high magnetic fields are used to identify a tilt of the complex and its hard anisotropy axis with respect to the surface normal. Electron injection into the substrate near the molecular rows induces a transition to a state with larger inelastic cross section, leaving the spin state unchanged.

Controlling the Spin States of FeTBrPP on Au(111).

Spin-flip excitations of iron porphyrin molecules on Au(111) are investigated with a low-temperature scanning tunneling microscope. The molecules adopt two distinct adsorption configurations on the surface that exhibit different magnetic anisotropy energies. Density functional theory calculations show that the different structures and excitation energies reflect unlike occupations of the Fe 3d levels. We demonstrate that the magnetic anisotropy energy can be controlled by changing the adsorption site, the orientation, or the tip-molecule distance.