The Magnetic Behaviour of CoTPP Supported on Coinage Metal Surfaces in the Presence of Small Molecules: A Molecular Cluster Study of the Surface trans-Effect

Density functional theory, combined with the molecular cluster model, has been used to investigate the surface trans-effect induced by the coordination of small molecules L (L = CO, NH3, NO, NO2 and O-2) on the cobalt electronic structure of cobalt tetraphenylporphyrinato (CoTPP) surface-supported on coinage metal surfaces (Cu, Ag, and Au). Regardless of whether L has a closed- or an open-shell electronic structure, its coordination to Co takes out the direct interaction between Co and the substrate eventually present. The CO and NH3 bonding to CoTPP does not influence the Co local electronic structure, while the NO (NO2 and O-2) coordination induces a Co reduction (oxidation), generating a 3d(8) Co-I (3d(6) Co-III) magnetically silent closed-shell species. Theoretical outcomes herein reported demonstrate that simple and computationally inexpensive models can be used not only to rationalize but also to predict the effects of the Co-L bonding on the magnetic behaviour of CoTPP chemisorbed on coinage metals. The same model may be straightforwardly extended to other transition metals or coordinated molecules.

Automated summary

The coordination of small molecules L (L = CO, NH3, NO, NO2 and O-2) to cobalt tetraphenylporphyrinato (CoTPP) was studied using density functional theory combined with the molecular cluster model. It was found that the coordination can significantly alter the magnetic behavior of cobalt.