Magnetic subunits within a single molecule–surface hybrid

Magnetic molecule–surface hybrids are ideal building blocks for molecular spintronic devices due to their appealing tailorable magnetic properties and nanoscale size. So far, assemblies of interacting molecular-surface hybrids needed for spintronic functionality were generated by depositing aromatic molecules onto transition-metal surfaces, resulting in a random arrangement of hybrid magnets due to the inherent and strong hybridization. Here, we demonstrate the formation of multiple intramolecular subunits within a single molecule–surface hybrid by means of spin-polarized scanning tunneling microscopy experiments and ab initio density functional theory calculations. This novel effect is realized by depositing a polycyclic aromatic molecule on a magnetic surface. A highly asymmetric chiral adsorption position induces different structural, electronic, and magnetic properties in each aromatic ring of the molecule. In particular, the induced molecular spin polarization near the Fermi energy varies among the rings due to site- and spin-dependent molecule–surface hybridization. Our results showcase a possible organic chemistry route of tailoring geometrically well-defined assemblies of magnetically distinguishable subunits in molecule–surface hybrids.

[1]  S. Blügel,et al.  Exchange interactions of magnetic surfaces below two-dimensional materials , 2016 .

[2]  M. Alouani,et al.  High Spin Polarization at Ferromagnetic Metal-Organic Interfaces: A Generic Property. , 2016, The journal of physical chemistry letters.

[3]  S. Blügel,et al.  Molecular induced skyhook effect for magnetic interlayer softening , 2015 .

[4]  Xingqiang Shi,et al.  Manipulating Magnetism at Organic/Ferromagnetic Interfaces by Molecule-Induced Surface Reconstruction. , 2015, Journal of the American Chemical Society.

[5]  L. Wan,et al.  Two-dimensional chiral molecular assembly on solid surfaces: formation and regulation , 2015 .

[6]  S. Blügel,et al.  Chemically functionalized magnetic exchange interactions of hybrid organic-ferromagnetic metal interfaces , 2015 .

[7]  Xingqiang Shi,et al.  Intramolecularly resolved Kondo resonance of high-spin Fe(II)-porphyrin adsorbed on Au(111) , 2015 .

[8]  S. Blügel,et al.  Long-range magnetic coupling between nanoscale organic-metal hybrids mediated by a nanoskyrmion lattice. , 2014, Nature nanotechnology.

[9]  Stefan Blügel,et al.  Magnetic hardening induced by nonmagnetic organic molecules. , 2013, Physical review letters.

[10]  S. Heinze,et al.  Atomic-scale inversion of spin polarization at an organic-antiferromagnetic interface , 2013, 1308.0934.

[11]  M. Cinchetti,et al.  Spin-dependent trapping of electrons at spinterfaces , 2013, Nature Physics.

[12]  J. Moodera,et al.  Interface-engineered templates for molecular spin memory devices , 2013, Nature.

[13]  S. Blügel,et al.  Atomic-scale magnetism of cobalt-intercalated graphene , 2013 .

[14]  A. Smogunov,et al.  Large magnetoresistance through a single molecule due to a spin-split hybridized orbital. , 2012, Nano letters.

[15]  R. Wiesendanger,et al.  Realizing All-Spin–Based Logic Operations Atom by Atom , 2011, Science.

[16]  P. Ordejón,et al.  Orbital specific chirality and homochiral self-assembly of achiral molecules induced by charge transfer and spontaneous symmetry breaking. , 2010, Physical review letters.

[17]  S. Ulloa,et al.  Spatially extended Kondo state in magnetic molecules induced by interfacial charge transfer. , 2010, Physical review letters.

[18]  R. Wiesendanger,et al.  Bulk Cr tips with full spatial magnetic sensitivity for spin-polarized scanning tunneling microscopy , 2010 .

[19]  M. Alouani,et al.  Impact on interface spin polarization of molecular bonding to metallic surfaces. , 2010, Physical review letters.

[20]  S. Blügel,et al.  Design of the local spin polarization at the organic-ferromagnetic interface. , 2010, Physical review letters.

[21]  S. Blügel,et al.  Spin- and energy-dependent tunneling through a single molecule with intramolecular spatial resolution. , 2010, Physical review letters.

[22]  A. Fert,et al.  Unravelling the role of the interface for spin injection into organic semiconductors , 2010, 1005.1826.

[23]  M. Cinchetti,et al.  Determination of spin injection and transport in a ferromagnet/organic semiconductor heterojunction by two-photon photoemission. , 2009, Nature materials.

[24]  A. Seitsonen,et al.  Supramolecular control of the magnetic anisotropy in two-dimensional high-spin Fe arrays at a metal interface. , 2009, Nature materials.

[25]  S. Blügel,et al.  Chemical versus van der Waals Interaction: the role of the heteroatom in the flat absorption of aromatic molecules C6H6, C5NH5, and C4N2H4 on the Cu(110) surface. , 2008, Physical review letters.

[26]  S. Heinze,et al.  On the preparation and electronic properties of clean W(1 1 0) surfaces , 2007 .

[27]  T. Ramsvik,et al.  Induced magnetic ordering in a molecular monolayer , 2005 .

[28]  S. M. Barlow,et al.  Complex organic molecules at metal surfaces: bonding, organisation and chirality , 2003 .

[29]  Valentin Dediu,et al.  Room temperature spin polarized injection in organic semiconductor , 2002 .

[30]  D. Moffatt,et al.  Determination of the absolute chirality of individual adsorbed molecules using the scanning tunnelling microscope , 1998, Nature.

[31]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[32]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[33]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[34]  U. Köhler,et al.  Misfit-related effects in the epitaxial growth of iron on W(110) , 1995 .

[35]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[36]  Hafner,et al.  Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. , 1994, Physical review. B, Condensed matter.

[37]  H. Güntherodt,et al.  Observation of vacuum tunneling of spin-polarized electrons with the scanning tunneling microscope. , 1990, Physical review letters.

[38]  D. Hamann,et al.  Theory and Application for the Scanning Tunneling Microscope , 1983 .

[39]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[40]  P. Hohenberg,et al.  Inhomogeneous Electron Gas , 1964 .

[41]  S. Chiang.  Molecular Imaging by STM , 1992 .