Site-specific bonding of copper adatoms to pyridine end groups mediating the formation of two-dimensional coordination networks on metal surfaces

We study the formation of a coordination network consisting of the organic pyridine-based 2,4,6-tris(4-pyridine)- 1,3,5-triazine (T4PT) species and Cu atoms on Cu(111) and Ag(111) metal surfaces. Using scanning tunneling microscopy, we find that the organic molecule T4PT forms stable two-dimensional porous networks on the surface of Cu(111) and, by codeposition of Cu atoms, also on the Ag(111) crystal, in which Cu atoms are twofold coordinated by T4PT molecules. X-ray absorption spectroscopy measurements of the metal-organic network Cu-T4PT on Ag(111) accompanied by density-functional theory calculations show that the nitrogen atoms of the pyridine end groups of the T4PT molecules are the active sites in coordinating the Cu adatoms. X-ray magnetic circular dichroism experiments reveal that the Cu atom in such a metal-organic motif is in a low-valent d(10) state and has no magnetic moment.