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.