XAS and XMCD Investigation of Mn12 Monolayers on Gold

The deposition of Mn12 single molecule magnets on gold surfaces was studied for the first time using combined X‐ray absorption spectroscopy (XAS) and X‐ray magnetic circular dichroism (XMCD) methods at low temperature. The ability of the proposed approach to probe the electronic structure and magnetism of Mn12 complexes without significant sample damage was successfully checked on bulk samples. Detailed information on the oxidation state and magnetic polarization of manganese ions in the adsorbates was obtained from XAS and XMCD spectra, respectively. Partial reduction of metal ions to MnII was clearly observed upon deposition on Au(111) of two different Mn12 derivatives bearing 16‐acetylthio‐hexadecanoate and 4‐(methylthio)benzoate ligands. The average oxidation state, as well as the relative proportions of MnII, MnIII and MnIV species, are strongly influenced by the deposition protocol. Furthermore, the local magnetic polarizations are significantly decreased as compared with bulk Mn12 samples. The results highlight an utmost redox instability of Mn12 complexes at gold surfaces, presumably accompanied by structural rearrangements, which cannot be easily revealed by standard surface analysis based on X‐ray photoelectron spectroscopy and scanning tunnelling microscopy. Cold experiments: The first low temperature XAS/XMCD study of Mn12 adsorbates on gold reveals an intrinsic redox‐instability of the clusters (see figure) and highlights the potential of the XAS/XMCD technique to probe the behaviour of molecular magnets at surfaces.