Orthogonal insertion of lanthanide and transition-metal atoms in metal-organic networks on surfaces

The orthogonal coordinative properties of tetrapyrrole macrocycles and nitrile ligands have been used in a multistep procedure towards interfacial d-f hetero-bimetallic nanoarchitectures based on a free-base porphyrin derivative functionalized with meso-cyanobiphenylene substituents. Molecular-level scanning tunneling microscopy studies reveal that the porphyrin module alone self-assembles on Ag(111) in a close-packed layer with a square unit cell. Upon co-deposition of Gd atoms, a square-planar motif is formed that reflects the fourfold coordination of CN ligands to the rare-earth centers. The resulting nanoporous network morphology is retained following exposure to a beam of Co atoms, which induces selective porphyrin metalation and ultimately yields a gridlike 2D metallosupramolecular architecture. Surface-confined d-f bimetallic 2D coordination nanosystems have been achieved by using a three-step procedure that exploits orthogonal coordination interactions of CN-functionalized free-base porphyrin linkers with rare-earth and transition-metal centers. By systematic STM investigations the assembly process was established and the resulting nanoarchitectures characterized at the molecular level.