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Learning the art of exploiting the interplay between different units at the atomic scale is a fundamental step in the realization of functional nano-architectures and interfaces. In this context, understanding and controlling the magnetic coupling between molecular centers and their environment is still a challenging task. Here we present a combined experimental-theoretical work on the prototypical case of the bis(phthalocyaninato)-lanthanide(III) (LnPc2) molecular nanomagnets magnetically coupled to a Ni substrate. By means of X-ray magnetic circular dichroism we show how the coupling strength can be tuned by changing the Ln ion. The microscopic parameters of the system are determined by ab-initio calculations and then used in a spin Hamiltonian approach to interpret the experimental data. By this combined approach we identify the features of the spin communication channel: the spin path is first realized by the mediation of the external (5d) electrons of the Ln ion, keeping the characteristic features of the inner 4 f orbitals unaffected, then through the organic ligand, acting as a bridge to the external world.

An austenite-martensite transition was observed in a 100-nm-thick Ni51.6Mn32.9Sn15.5 film by temperature-dependent resistivity and magnetization measurements, revealing a martensite starting temperature of M-S approximate to 260 K. The influence of the structural phase transition on the electronic structure and the magnetic properties was studied element specifically employing temperature-dependent x-ray-absorption spectroscopy and x-ray magnetic circular dichroism. In addition, density functional theory calculations have been performed to study the electronic and magnetic properties of both phases. It is shown that off-stoichiometric Ni-Mn-Sn alloys can exhibit a substantial magnetocrystalline anisotropy energy in the martensite phase. For Mn a change of the electronic structure and a strong increase of the ratio of orbital to spin magnetic moment m(l)/m(S) can be observed, whereas for Ni nearly no changes occur. Applying an external magnetic field of B = 3 T reverses the change of the electronic structure of Mn and reduces the ratio of m(l)/m(S) from 13.5 to approximate to 1 % indicating a field-induced reverse martensitic transition.

Different magnetic coupling mechanisms have been identied for a few monolayers of Co-porphyrin molecules deposited on a graphene covered Ni(111) single crystal. A relatively strong antiferromagnetic coupling of the first molecular layer via graphene to the Ni crystal in comparison to a weaker inter-molecular coupling gives rise to a complex field-dependent response of this hybrid system. By continuously increasing the magnetic eld strength the net magnetization of the molecular system switches from antiparallel to parallel to the field direction at 2.5 T. Utilizing x-ray absorption spectroscopy and x-ray magnetic circular dichroism, the element specic magnetization and field dependence was probed. The nature of the magnetic couplings is identied by means of density functional theory and orbital dependent susceptibilities.

The coupling of submonolayer coverages of Fe-phthalocyanine molecules on bare and oxygen-covered ferromagnetic Co(001) films was studied by x-ray-absorption spectroscopy, especially the x-ray magnetic circular dichroism, in combination with density functional theory. We observe that the magnetic moments of the paramagnetic molecules are aligned even at room temperature, resulting from a magnetic coupling to the substrate. While the magnetization of the Fe ions directly adsorbed on the Co surface is parallel to the magnetization of the Co film, the introduction of an oxygen interlayer leads to an antiparallel alignment. As confirmed by theory, the coupling strength is larger for the system FePc/Co than for FePc/O/Co, causing a stronger temperature dependence of the Fe magnetization for the latter system. Furthermore, the calculations reveal that the coupling mechanism changes due to the O layer from mostly direct exchange to Co of the bare surface to a 180 degrees antiferromagnetic superexchange via the O atoms. Finally, by comparing the experimental x-ray-absorption spectra at the N K edge with the corresponding calculations, the contribution of the individual orbitals has been determined and the two inequivalent N atoms of the molecules could be distinguished.