Abstract
Fe(II) spin-crossover systems can be quantitatively converted from the low-spin (LS) to the high-spin (HS) state well below the thermal transition temperature by irradiating either into the metal-ligand charge transfer or d-d absorption bands, and even in low-spin systems a transient population of the HS state can be achieved. This fact can be made use of to determine HS → LS relaxation rate constants for a wide variety of Fe(II) spin-crossover and low-spin systems. The HS → LS relaxation shows strong deviations from an Arrhenius behaviour, with nearly temperature-independent tunnelling below ∼70 K and a thermally activated process above ∼100 K. The range of more than 12 orders of magnitude in the low temperature tunnelling rate constant can be understood in terms of a non-adiabatic multiphonon process, where in the strong vibronic coupling limit an inverse energy gap law holds.
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Hauser, A., Adler, P., Deisenroth, S. et al. Intersystem crossing in Fe(II) coordination compounds. Hyperfine Interact 90, 77–87 (1994). https://doi.org/10.1007/BF02069119
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DOI: https://doi.org/10.1007/BF02069119