Fascinating electronic games in iron complexes

Coordination compounds of transition metal ions with open-shell electron configurations may exhibit dynamic electronic-structure phenomena, depending on the nature of the coordinating ligand sphere. The change of spin state with temperature (thermal spin-crossover), light-induced electron transfer processes leading to long-lived metastable charge and spin states (e.g. LIESST effect), are some of the fascinating electronic games encountered in transition metal compounds, which are presently under extensive study by chemists and physicists. Moessbauer spectroscopy plays a dominant role in the investigation of such phenomena in iron compounds, as will be demonstrated in this paper. This work will focus on selected examples of thermal spin-crossover in iron(II) complexes and switching between different spin states by irradiation with light of different wavelength (LIESST effect), demonstrating that Moessbauer spectroscopy besides other physical techniques proves to be a highly elegant tool for following the spin state conversion and the concomitant changes of molecular and crystal structure properties. Finally, Moessbauer emission spectroscopy, both time integral and time differential, has been employed to generate and identify long-lived excited spin states by making use of the nuclear disintegration of 57Co as an intrinsic molecular light source (NIESST, nuclear decay-induced excited-spin-state trapping). Lifetime measurements by optical techniques on LIESST states and by time-differential Moessbauer coincidence spectroscopy on NIESST states prove that the relaxation pathways in the mechanisms for LIESST and NIESST are identical