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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The amplitude of the extended x-ray-absorption fine structure of concentrated samples measured in the fluorescence mode (FLEXAFS) as well as the overall shape of the fluorescence-yield spectra strongly depend on the detection geometry through the self-absorption effect. In these cases, a conventional EXAFS analysis can lead to systematic errors in the determination of physical parameters. We studied the distortions in the FLEXAFS spectra through the self-absorption effect measuring the FLEXAFS of a NiO single crystal above the oxygen E edge for various detection geometries. We show that knowing the stoichiometry of the sample we can fully correct for the self-absorption efFect using a simple theory and obtain the correct, geometry-independent oxygen EXAFS of NiO. The correction procedure presented here for the prototype system of NiO is generally applicable and should be the first step in the analysis of FLEXAFS data of concentrated samples. We calculate the information depth of the fluorescence detection as a function of the experimental geometry. The knowledge of the self-absorption in relationship to the information depth allows the determination of the optimum experimental setup.

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We demonstrate that an antiferromagnetic coupling between paramagnetic Fe-porphyrin molecules and ultrathin Co and Ni magnetic films on Cu(100) substrates can be established by an intermediate layer of atomic oxygen. The coupling energies have been determined from the temperature dependence of x-ray magnetic circular dichroism measurements. By density functional theory+U calculations the coupling mechanism is shown to be superexchange between the Fe center of the molecules and Co surface-atoms, mediated by oxygen.