In the field of molecular spintronics, the use of magnetic molecules for information technology is a main target and the observation of magnetic hysteresis on individual molecules organized on surfaces is a necessary step to develop molecular memory arrays. Although simple paramagnetic molecules can show surface-induced magnetic ordering and hysteresis when deposited on ferromagnetic surfaces, information storage at the molecular level requires molecules exhibiting an intrinsic remnant magnetization, like the so-called single-molecule magnets (SMMs). These have been intensively investigated for their rich quantum behaviour but no magnetic hysteresis has been so far reported for monolayers of SMMs on various non-magnetic substrates, most probably owing to the chemical instability of clusters on surfaces. Using X-ray absorption spectroscopy and X-ray magnetic circular dichroism synchrotron-based techniques, pushed to the limits in sensitivity and operated at sub-kelvin temperatures, we have now found that robust, tailor-made Fe(4) complexes retain magnetic hysteresis at gold surfaces. Our results demonstrate that isolated SMMs can be used for storing information. The road is now open to address individual molecules wired to a conducting surface in their blocked magnetization state, thereby enabling investigation of the elementary interactions between electron transport and magnetism degrees of freedom at the molecular scale.

A fundamental step towards atomic- or molecular-scale spintronic devices has recently been made by demonstrating that the spin of an individual atom deposited on a surface, or of a small paramagnetic molecule embedded in a nanojunction, can be externally controlled. An appealing next step is the extension of such a capability to the field of information storage, by taking advantage of the magnetic bistability and rich quantum behaviour of single-molecule magnets (SMMs). Recently, a proof of concept that the magnetic memory effect is retained when SMMs are chemically anchored to a metallic surface was provided. However, control of the nanoscale organization of these complex systems is required for SMMs to be integrated into molecular spintronic devices. Here we show that a preferential orientation of Fe(4) complexes on a gold surface can be achieved by chemical tailoring. As a result, the most striking quantum feature of SMMs-their stepped hysteresis loop, which results from resonant quantum tunnelling of the magnetization-can be clearly detected using synchrotron-based spectroscopic techniques. With the aid of multiple theoretical approaches, we relate the angular dependence of the quantum tunnelling resonances to the adsorption geometry, and demonstrate that molecules predominantly lie with their easy axes close to the surface normal. Our findings prove that the quantum spin dynamics can be observed in SMMs chemically grafted to surfaces, and offer a tool to reveal the organization of matter at the nanoscale.

Using X-ray absorption techniques, we show that temperature-and light-induced spin crossover properties are conserved for a sub-monolayer of the [Fe(H 2 B(pz) 2 ) 2 (2,2'-bipy)] complex evaporated onto a Au(111) surface. For a significant fraction of the molecules, we see changes in the absorption at the L 2,3 edges that are consistent with those observed in bulk and thick film references. Assignment of these changes to spin crossover is further supported by multiplet calculations to simulate the x-ray absorption spectra. As others have observed in experiments on monolayer coverages, we find that many molecules in our submonolayer system remain pinned in one of the two spin states. Our results clearly demonstrate that temperature-and light-induced spin-crossover is possible for isolated molecules on surfaces, but that interactions with the surface may play a key role in determining when this can occur. TOC X-ray absorption techniques evidenced that temperature-and light-induced spin crossover properties were conserved for a sub-monolayer of the [Fe(H 2 B(pz) 2 ) 2 (2,2'-bipy)] complex evaporated on a Gold surface KEYWORDS: spin crossover,·UHV evaporation,·submonolayer,·X-ray absorption,·iron complexes 3 Spin Crossover (SCO) complexes are promising building blocks for spintronic 1 Using variable temperature X-ray absorption spectra, we examined a submonolayer coverage evaporated in situ under UHV conditions on Au(111), before and after irradiation with visible laser light. We compare these results to those obtained from two other samples: 1) a 5 single crystal finely scratched on gold foil, which we use as a spectroscopic bulk reference; and 2) a 300 nm thick film sublimedex situ on copper foil, to check the preservation of structure and properties of the complex. Experimental spectra were then compared to the ones obtained using multiplet calculations. 37-39The variation of the L 2,3 edge spectra for the bulk sample over the range of the thermal spin crossover (100-300 K) is reported in Figure 1a(see also Figure S1 in Supplementary Information Spectra measured on the thick film prepared ex situ are similar to the bulk, and show comparable temperature dependence (Figure 1b and Figure S1). Nevertheless, the thick film spectrum is slightly differentfrom the bulk compound: shoulders on the high-energy side (at 300 K) or at the low-energy side (at 100 K) of the L 3 absorption peak, are likely associated with a small fraction of decomposition product, which maybe caused by air exposure of this sample prepared ex situ.The analysis of the temperature-dependent spectra as weighted sums of the bulk spectra at 300 K and 100 K, chosen as representative of the HS and LS state respectively, allows for the extraction of the temperature dependence of the HS fraction (Table S2). For the thick film, the shoulder signals were found to be temperature independent, and thus do not affect the switching behavior. We extracted this spurious contribution ( Figures S3 and S4) and subtracted it from all spectra before evaluating...

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Successful attempts to deposit SMMs in UHV conditions\ud have been carried out with a tetranuclear iron(III) cluster [ 9 ]\ud and lanthanide bis-phthalocyaninato (LnPc 2 ) complexes. [ 10 , 11 ]\ud For the latter the seminal works of Ishikawa et al. [ 12 ] showed\ud that slow dynamics of the magnetization in these mononuclear\ud complexes is originated directly from their strong single ion\ud anisotropy. Very recently a structural and magnetic characterization\ud of a sub-monolayer deposit TbPc 2 based on synchrotronlight\ud techniques has confi rmed that this magnetic anisotropy is\ud retained on surface. [ 13 ] The absence of the observation of typical\ud slow dynamics of the magnetization has been attributed to the\ud long time-scale of the X-ray based experiments.\ud We report here a synchrotron-based investigation on neutral\ud TbPc 2 evaporated thick and thin fi lms evidencing that the thick\ud fi lm of TbPc 2 is characterized by slow relaxation of the magnetization\ud and opening of a butterfl y hysteresis cycle at temperatures\ud as high as 15 K but not observed for the thin fi lm. These\ud differences are accompanied with a drastic change in the orientation\ud of the TbPc 2 molecules in the two fi lm

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The deposition of Mn(12) 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 Mn(12) 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 Mn(II) was clearly observed upon deposition on Au(111) of two different Mn(12) derivatives bearing 16-acetylthio-hexadecanoate and 4-(methylthio)benzoate ligands. The average oxidation state, as well as the relative proportions of Mn(II), Mn(III) and Mn(IV) species, are strongly influenced by the deposition protocol. Furthermore, the local magnetic polarizations are significantly decreased as compared with bulk Mn(12) samples. The results highlight an utmost redox instability of Mn(12) 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.

X-ray absorption spectra at the Co L(2,3)-edges were analyzed by means of ligand field multiplet calculations in different states of three photomagnetic CoFe Prussian blue analogues of chemical formula Cs(2)Co(4)[Fe(CN)(6)](3.3) x 11 H(2)O, Rb(2)Co(4)[Fe(CN)(6)](3.3) x 11 H(2)O and Na(2)Co(4)[Fe(CN)(6)](3.3) x 11 H(2)O. These simulations of the experimental spectra allowed the quantification of the crystal field parameter (10Dq). This determination led us (i) to evidence different behaviors of the Co(III)(LS) and Co(II)(HS) ions in the three-dimensional structure related to their electronic configurations, (ii) to propose an approach based on the electronic density distribution along the Co-NC-Fe linkage to account for the energy position of the states implied in the switching properties of the compounds, and (iii) to explain the different photomagnetic properties observed as a function of the size of the inserted alkali cation by competing interactions between the cyanide ion and the transition metal ions within the CoFe cyanide bimetallic network on the one hand and the cyanide ion and the alkali metal ions on the other hand.