Orthogonal Insertion of Lanthanide and Transition-Metal Atoms in Metal-Organic Networks on Surfaces

J. I. Urgel, D. Ecija, W. Auwaerter, D. Stassen, D. Bonifazi, J. V. Barth,
Angew. Chem., Int. Ed. 2015, 54, 6163-6167
DOI: 10.1002/anie.201410802


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.

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