The growth of a fullerene derivative (PCBM) on top of a layer of a tetrathiafulvalene (TTF) derivative previously deposited on Au(111) has been studied by scanning tunneling microscopy (STM). The results show that the preferential interaction with the gold substrate induces the exchange of PCBM molecules with the exTTF monolayer, expelling exTTF molecules to the outer surface. This exchange process is forbidden when the thickness of the exTTF layer increases above the monolayer, and the larger surface energy of PCBM leads to the growth of 3D islands ; Our work was supported by the MICINN of Spain (FIS2010-18847, FIS2012-33011), Comunidad de Madrid (NanobiomagnetS2009/MAT-1726), CONSOLIDER-INGENIO on Molecular Nanoscience (CSD2007-00010) and European Union (SMALL PITN-GA- 2009-23884)
TCNQ derivatives adsorbed on a metal surface undergo a self-limited decyanation reaction that only affects two out of the four cyano groups in the molecule. Combined Scanning Tunneling Microscopy/X-ray Photoelectron Spectroscopy experiments and Density Functional Theory calculations relate the self-limiting behavior to the transfer of electrons from the metal to the molecule ; We thank the CCC-UAM and the RES for allocation of computer time. Our work has been supported by the MINECO of Spain (MAT2009-13488, FIS2010-18847, FIS2010-15127, FIS2012-33011, CTQ2010-17006, CTQ2011-24652/BTQ), Comunidad de Madrid (Nanobiomagnet S2009/MAT-1726, Madrisolar-2 S2009/PPQ-1533), CONSOLIDER-INGENIO on Molecular Nanoscience (CSD2007- 00010) and European Union (SMALL PITN-GA-2009-23884)
Taming the magnetic anisotropy of lanthanides through coordination environments is crucial to take advantage of the lanthanides properties in thermally robust nanomaterials. In this work, the electronic and magnetic properties of Dy-carboxylate metal–organic networks on Cu(111) based on an eightfold coordination between Dy and ditopic linkers are inspected. This surface science study based on scanning probe microscopy and X-ray magnetic circular dichroism, complemented with density functional theory and multiplet calculations, reveals that the magnetic anisotropy landscape of the system is complex. Surface-supported metal–organic coordination is able to induce a change in the orientation of the easy magnetization axis of the Dy coordinative centers as compared to isolated Dy atoms and Dy clusters, and significantly increases the magnetic anisotropy. Surprisingly, Dy atoms coordinated in the metallosupramolecular networks display a nearly in-plane easy magnetization axis despite the out-of-plane symmetry axis of the coordinative molecular lattice. Multiplet calculations highlight the decisive role of the metal–organic coordination, revealing that the tilted orientation is the result of a very delicate balance between the interaction of Dy with O atoms and the precise geometry of the crystal field. This study opens new avenues to tailor the magnetic anisotropy and magnetic moments of lanthanide elements on surfaces. ; The ALBA synchrotron is acknowledged for providing beam time at BOREAS beamline (proposal number 2015091454). This project has received funding from the European Research Council (ERC, grant 766555) and Marie Sklodowska-Curie Actions (MSCA, project 894924) under the European Union's Horizon 2020 research and innovation programme. This work has been financed by the Spanish Ministerio de Economía, Industria y Competitividad (projects FIS2016-78591-C3-1-R, RTI2018-097895-B-C42, MAT2016-78293-C6-2-R, MAT2017-85089-C2-1-R, and PID2019-107338RB-C65); the Comunidad de Madrid (Projects S2013/MIT-2850, P2018/NMT4321, and S2018/NMT-4367); the European Regional Development Fund (ERDF) under the program Interreg V-A España-Francia-Andorra (Contract No. EFA 194/16 TNSI); and "Severo Ochoa" Programme for Centres of Excellence in R&D (grants SEV-2016-0686, and SEV-2017-0706).
