Preservation of electronic properties of double-decker complexes on metallic supports

Single-molecule magnets based on lanthanide double-deckers are attracting significant attention due to their unrivaled single-ion anisotropy. To exploit their fascinating electronic and magnetic properties in devices for information storage or spin transport, studies on the preservation or variation of electronic and magnetic functionalities upon adsorption on surfaces are necessary. Herein, we introduced a comprehensive scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) surface science study, complemented by density functional theory (DFT) simulations, of a recently synthesized single-molecule magnet based on porphyrazine deckers, conveniently equipped with ethyl moieties to make them soluble and sublimable. We demonstrated that the double-decker species were intactly adsorbed on Au(111), Ag(111), and Cu(111) in a flat-on fashion and self-assembled in hexagonal close-packed layers. Systematic multi- and monolayer XPS was performed on the surface-confined species, confirming the preservation of the electronic properties of the ligands and the lanthanide center upon adsorption.We acknowledge the financial support received from the EU (projects ERC Advanced Grant MolArt (no. 247299), ERC Consolidator Grant Nanosurfs (no. 615233), ERC Starting Grant CHEMCOMP (no. 279313), EC FP7-PEOPLE-2011-COFUND AMAROUT II program), the Spanish Ministerio de Economía y Competitividad (MINECO) (RYC-2012-11133, FIS 2013-40667-P, FIS 2015-67287-P and Severo Ochoa Excellence Accreditation 2014-2018 SEV-2013-0319), the Comunidad de Madrid (project MAD2D), Generalitat de Catalunya (2014-SGR-797), the IMDEA Foundation, the ICIQ Foundation, the German Research Foundation (DFG) via KL 2294/3-1, and the Munich-Center for Advanced Photonics (MAP). WA acknowledges funding received by the DFG via a Heisenberg professorship