Light‐induced spin‐state switching is one of the most attractive properties of spin‐crossover materials. In bulk, low‐spin (LS) to high‐spin (HS) conversion via the light‐induced excited spin‐state trapping (LIESST) effect may be achieved with a visible light, while the HS‐to‐LS one (reverse‐LIESST) requires an excitation in the near‐infrared range. Now, it is shown that those phenomena are strongly modified at the interface with a metal. Indeed, an anomalous spin conversion is presented from HS state to LS state under blue light illumination for FeII spin‐crossover molecules that are in direct contact with metallic (111) single‐crystal surfaces (copper, silver, and gold). To interpret this anomalous spin‐state switching, a new mechanism is proposed for the spin conversion based on the light absorption by the substrate that can generate low energy valence photoelectrons promoting molecular vibrational excitations and subsequent spin‐state switching at the molecule–metal interface.
Spin-crossover molecules are very attractive compounds to realize multifunctional spintronic devices. Understanding their properties when deposited on metals is therefore crucial for their future rational implementation as ultrathin films in such devices.Using X-ray absorption spectroscopy, we study the thermal transition of the spincrossover compound Fe II ((3,5-(CH 3 ) 2 Pz) 3 BH) 2 from submonolayer to multilayers on a Cu(111) substrate. We determine how the residual fraction of high spin molecules at low temperature as well as the bistability range and the temperature of switching depend on the layer thickness. The most spectacular effect is the clear opening of a 35±9 K thermal hysteresis loop for a 3.0±0.7 monolayers thick film. In order to better understand the role played by the substrate and the dimensionality on the thermal bistability, we have performed Monte Carlo Arrhenius simulations in the framework of a mechanoelastic model that include a molecule-substrate interaction. This model reproduces well the main features observed experimentally and can predict how the spin-crossover transition is modified by the thickness and the substrate interaction.
Graphical TOC EntryFor thin films down to three-monolayer thick, spin-crossover molecules present an thermal hysteresis when adsorbed on Cu(111).
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