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

By José I Urgel, David Ecija, Willi Auwärter, Daphné Stassen, Davide Bonifazi and Johannes V. Barth


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

Topics: d-f metal-organic networks, lanthanides, orthogonal interactions, porphyrinoids, scanning tunneling microscopy, transition metals, Chemistry (all), Catalysis
Year: 2015
DOI identifier: 10.1002/(ISSN)1521-3773
OAI identifier: oai:arts.units.it:11368/2869722
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