title: Orthogonal insertion of lanthanide and transition-metal atoms in metal-organic networks on surfaces.
abstract: 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.
authors.affiliation: Physik Department E20, Technische Universität München, 85748 Garching, München (Germany).
authors.forename: José I
authors.initials: JI
authors.lastname: Urgel
authors.affiliation: Physik Department E20, Technische Universität München, 85748 Garching, München (Germany). david.ecija@imdea.org.|IMDEA Nanoscience, 28049 Madrid (Spain). david.ecija@imdea.org.
authors.forename: David
authors.initials: D
authors.lastname: Ecija
authors.affiliation: Physik Department E20, Technische Universität München, 85748 Garching, München (Germany). wau@tum.de.
authors.forename: Willi
authors.initials: W
authors.lastname: Auwärter
authors.affiliation: Namur Research College (NARC) and Department of Chemistry University of Namur (UNamur), Rue de Bruxelles 61, Namur 5000 (Belgium).
authors.forename: Daphné
authors.initials: D
authors.lastname: Stassen
authors.affiliation: Namur Research College (NARC) and Department of Chemistry University of Namur (UNamur), Rue de Bruxelles 61, Namur 5000 (Belgium). davide.bonifazi@unamur.be.|Department of Pharmaceutical and Chemical Sciences and INSTM UdR Trieste, University of Trieste, Piazzale Europa 1, Trieste 34127 (Italy). davide.bonifazi@unamur.be.
authors.forename: Davide
authors.initials: D
authors.lastname: Bonifazi
authors.affiliation: Physik Department E20, Technische Universität München, 85748 Garching, München (Germany).
authors.forename: Johannes V
authors.initials: JV
authors.lastname: Barth
keywords: d-f metal-organic networks; lanthanides; orthogonal interactions; porphyrinoids; scanning tunneling microscopy; transition metals