Abstract
To realize molecular spintronic devices, it is important to externally control the magnetization of a molecular magnet. One class of materials particularly promising as building blocks for molecular electronic devices is the paramagnetic porphyrin molecule in contact with a metallic substrate. Here, we study the structural orientation and the magnetic coupling of in-situ-sublimated Fe porphyrin molecules on ferromagnetic Ni and Co films on Cu(100). Our studies involve X-ray absorption spectroscopy and X-ray magnetic circular dichroism experiments. In a combined experimental and computational study we demonstrate that owing to an indirect, superexchange interaction between Fe atoms in the molecules and atoms in the substrate (Co or Ni) the paramagnetic molecules can be made to order ferromagnetically. The Fe magnetic moment can be rotated along directions in plane as well as out of plane by a magnetization reversal of the substrate, thereby opening up an avenue for spin-dependent molecular electronics.
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References
Karki, L. et al. Electronic Stark effect studies of a porphyrin-based push–pull chromophore displaying a large first hyperpolarizability: State-specific contributions to β. J. Am. Chem. Soc. 120, 2606–2611 (1998).
LeCours, S. M. et al. Push–pull arylethynyl porphyrins: New chromophores that exhibit large molecular first-order hyperpolarizabilities. J. Am. Chem. Soc. 118, 1497–1503 (1996).
Barth, J. V., Costantini, G. & Kern, K. Engineering atomic and molecular nanostructures at surfaces. Nature 437, 671–679 (2005).
Maricondi, C., Swift, W. & Straub, D. K. Thermomagnetic analysis of hemin and related compounds. J. Am. Chem. Soc. 91, 5205–5210 (1969).
Kalish, H. et al. Meso substituent effects on the geometric and electronic structures of high-spin and low-spin iron(III) complexes of mono-meso-substituted octaethylporphyrins. Inorg. Chem. 41, 989–997 (2002).
Gottfried, J. M., Flechtner, K., Kretschmann, A., Lukasczyk, T. & Steinrück, H.-P. Direct synthesis of a metalloporphyrin complex on a surface. J. Am. Chem. Soc. 128, 5644–5645 (2006).
Goulon, J., Goulon-Ginet, Ch. & Gotte, V. in The Porphyrin Handbook Vol. 7 (eds Kadish, K. M., Smith, K. M. & Guilard, R.) (Academic, New York, 2000).
Okajima, T., Yamamoto, Y., Ouchi, Y. & Seki, K. NEXAFS spectra of metallotetraphenylporphyrins with adsorbed nitrogen monoxide. J. Electron. Spectroscop. Relat. Phenom. 114–116, 849–854 (2001).
Polzonetti, G. et al. Electronic structure of platinum complex-Zn-porphyrinato assembled macrosystems, related precursors and model molecules, as probed by X-ray absorption spectroscopy (NEXAFS): Theory and experiment. Chem. Phys. 296, 87–100 (2004).
Narioka, S. et al. XANES spectroscopic studies of evaporated porphyrin films: Molecular orientation and electronic structure. J. Phys. Chem. 99, 1332–1337 (1995).
Scheybal, A. et al. Induced magnetic ordering in a molecular monolayer. Chem. Phys. Lett. 411, 214–220 (2005).
Ghosh, A., Gonzalez, E., Vangberg, T. & Taylor, P. Molecular structures and electron distributions of higher-valent iron and manganese porphyrins. Density functional theory calculations and some preliminary open-shell coupled-cluster results. J. Porphyrins Phthalocyanines 5, 345–356 (2001).
Liao, M.-S. & Scheiner, S. Electronic structure and bonding in unligated and ligated FeII porphyrins. J. Chem. Phys. 116, 3635–3645 (2002).
Stöhr, J. et al. Liquid crystal alignment on carbonaceous surfaces with orientational order. Science 292, 2299–2302 (2001).
Wende, H. Recent advances in X-ray absorption spectroscopy. Rep. Prog. Phys. 67, 2105–2181 (2004).
Stöhr, J. NEXAFS Spectroscopy (Springer, Berlin, 1992).
Heijboer, W. M. et al. In-situ soft X-ray absorption of over-exchanged Fe/ZSM5. J. Phys. Chem. B 107, 13069–13075 (2003).
Hocking, R. K. et al. Fe L-edge X-ray absorption spectroscopy of low-spin heme relative to non-heme FE complexes: Delocalization of Fe d-electrons into the porphyrin ligand. J. Am. Chem. Soc. 129, 113–125 (2007).
Perdew, J. P. & Wang, Y. Accurate and simple analytic representation of the electron-gas correlation energy. Phys. Rev. B 45, 13244–13249 (1992).
Barlow, D. E., Scudiero, L. & Hipps, K. W. Scanning tunneling microscopy study of the structure and orbital-mediated tunneling spectra of cobalt(II) phthalocyanine and cobalt(II) tetraphenylporphyrin on Au(111): Mixed composition films. Langmuir 20, 4413–4421 (2004).
Leung, K. et al. Density functional theory and DFT+U study of transition metal porphine on Au(111) surfaces and effects of applied electric fields. J. Am. Chem. Phys. Soc. 128, 3659–3668 (2006).
Goodenough, J. B. Magnetism and the Chemical Bond (Wiley, New York, 1963).
Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Acknowledgements
Support by the BMBF (05 KS4 KEB/5), the DFG (Sfb658), the Swedish Research Council, the Foundation for Strategic Research and the Swedish National Infrastructure for Computing (SNIC) is gratefully acknowledged. One of us (H.W.) wishes to thank the DFG (Heisenberg fellowship) and Center for Dynamical Studies, Uppsala University, for hospitality and support during his stay in Uppsala. P.M.P. and P.M.O. acknowledge support through the EU network on molecular biosensors (MOT-Test). We thank B. Zada, W. Mahler and F. Senf for technical help during the beamtime.
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The experimental investigation was carried out at the Freie Universität, Berlin, whereas the theoretical research was carried out at Uppsala University. Both groups contributed equally to the work.
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Wende, H., Bernien, M., Luo, J. et al. Substrate-induced magnetic ordering and switching of iron porphyrin molecules. Nature Mater 6, 516–520 (2007). https://doi.org/10.1038/nmat1932
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DOI: https://doi.org/10.1038/nmat1932
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