Characterizing structural distortions in the metastable spin states of d⁴–d⁷ transition metal ion complexes is crucial to understand the nature of their bistability and eventually control their switching dynamics. In particular, the impact of the Jahn–Teller effect needs to be assessed for any electronic configuration that could be effectively degenerate, as in e.g. the high-spin (HS) manifold of highly symmetric homoleptic Fe^II complexes. However, capturing its manifestations remains challenging since crystallization generally alters the molecular conformations and their interconversion. With the rapid progress of ultrafast X-ray absorption spectroscopy, it is now possible to collect data with unprecedented signal-to-noise ratio, opening up for detailed structural characterization of transient species in the homogeneous solution phase. By combining the analysis of picosecond X-ray absorption spectra with DFT simulations, the structure of the photoinduced HS state is elucidated for solvated [Fe(terpy)₂]²⁺ (terpy = 2,2′:6′,2″-terpyridine). This species can be viewed as the average ⁵B structure in D₂ symmetry that originates from a dynamic Jahn–Teller effect in the HS manifold. These results evidence the active role played by this particular instance of vibronic coupling in the formation of the HS state for this benchmark molecule. Ultimately, correlating the interplay between intramolecular and intermolecular degrees of freedom to conformational strain and distortions in real time should contribute to the development of advanced functionalities in transition metal ion complexes.

The absorption spectra of Sm²⁺ doped in MFX (M=Sr, Ba; X=Cl, Br) crystals were studied within the range of 20,000–35,000 cm^−1 as a function of temperature and host. The absorption bands observed were described with a simple model developed by Wood and Kaiser using group theory. The temperature and host dependence on the ⁷F₀→⁵D₃ Fano resonance lines were investigated. BaFCl:Sm²⁺ system showed a “normalâ€� ⁷F₀→⁵D₃ transition at 4 K in spite of similar crystal structure and absorption profile with other MFX hosts. New Fano resonances were observed in the absorption spectra at higher energies (23,000–25,000 cm^−1) for all MFX:Sm²⁺ systems at 4 K which persist up to room temperature. Preliminary energy level calculation showed that these resonance lines involve the interaction between higher excited ⁵L_J states of 4 f⁶configuration and 4 f⁵5d¹ configuration.