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Orthogonal Insertion of Lanthanide and Transition‐Metal Atoms in Metal–Organic Networks on Surfaces
Author(s) -
Urgel José I.,
Ecija David,
Auwärter Willi,
Stassen Daphné,
Bonifazi Davide,
Barth Johannes V.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201410802
Subject(s) - porphyrin , bimetallic strip , metalation , scanning tunneling microscope , crystallography , metal , nitrile , chemistry , lanthanide , nanoporous , transition metal , materials science , photochemistry , nanotechnology , stereochemistry , organic chemistry , ion , catalysis
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.