Soft-x-ray-induced spin-state switching of an adsorbed Fe(II) spin-crossover complex

For probing the nature of spin-state switching in spin-crossover molecules adsorbed on surfaces, x-ray absorption spectroscopy has emerged as a powerful tool due to its high sensitivity and element selectivity in tracing even subtle electronic, magnetic, or chemical changes. However, the x-rays itself can induce a spin transition and might have unwanted influence while investigating the effect of other stimuli such as temperature or light, or of the surface, on the spin switching behaviour. Herein, we present the spin switching of an Fe(II) complex adsorbed on a highly oriented pyrolytic graphite surface with particular emphasis on the x-ray-induced switching. For a submonolayer coverage, the complex undergoes a complete and reversible temperature- and light-induced spin transition. The spin states are switched both ways by x-rays at 5 K, i.e. from the high-spin state to the low-spin state or vice versa, depending on the relative amount of each species. Furthermore, we quantify the fraction of molecules undergoing soft x-ray-induced photochemistry, a process which results in an irreversible low-spin state component, for a particular exposure time. This can be greatly suppressed by reducing the beam intensity.