Surface-Supported Robust 2D Lanthanide-Carboxylate Coordination Networks

Lanthanide-based metal-organic compounds and architectures are promising systems for sensing, heterogeneous catalysis, photoluminescence, and magnetism. Herein, the fabrication of interfacial 2D lanthanide-carboxylate networks is introduced. This study combines low- and variable-temperature scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS) experiments, and density functional theory (DFT) calculations addressing their design and electronic properties. The bonding of ditopic linear linkers to Gd centers on a Cu(111) surface gives rise to extended nanoporous grids, comprising mononuclear nodes featuring eightfold lateral coordination. XPS and DFT elucidate the nature of the bond, indicating ionic characteristics, which is also manifest in appreciable thermal stability. This study introduces a new generation of robust low-dimensional metallosupramolecular systems incorporating the functionalities of the f-block elements.Work was supported by the European Research Council Advanced Grant MolArt (Grant No. 247299), the Munich Center for Advanced Photonics (MAP), the Technische Universität München‐Institute for Advanced Study, funded by the German Research Foundation (DFG) via the German Excellence Initiative, and by the Comunidad Autónoma de Madrid (CAM) through project No. S2013/MIT‐3007 (MAD2D). D.E. thanks funding through the European Marie Curie Program COFUND project No. 291803 (AMARAOUT II) and the Spanish MINECO project RYC‐2012‐11133. Y.W., M.A., F.M. thank support by the Spanish MICINN projects FIS2013–42002‐R and CTQ2013–43698‐P, the CAM project NANOFRONTMAG‐CM ref. S2013/MIT‐2850, and the European COST Action CM1204 XLIC. W. A. acknowledges funding by the DFG via a Heisenberg professorship