In operando XAFS experiments on flexible electrochromic devices based on Fe(II)-metallo-supramolecular polyelectrolytes and vanadium oxide

Flexible electrochromic devices (ECDs) based on Fe(II)-metallo-supramolecular polyelectrolytes (Fe-MEPE) and vanadium oxide are studied in operando by means of x-ray absorption fine structure (XAFS) spectroscopy. The ECDs are blue-purple in the colored state at 0.0 V and become light yellow when a voltage of 1.6 V is applied. The XAFS studies at the K-edge of Fe(II) reveals that the absorption edge is shifted toward higher energies by 1.8 eV in the transparent state. Comparison of two different ECDs and different charge cycles demonstrates the reversibility and repeatability of the process. We attribute the shift to a charge transfer and a change of oxidation state of the ions from Fe2+ to Fe3+. The transition is not accompanied by a noticeable structural change of the octahedral coordination geometry as confirmed by analysis of the extended x-ray absorption fine structure (EXAFS) data.