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Local structure of Fe2+ and Fe3+ in organic solvents

We systematically investigated the local structure of Fe2+ and Fe3+ in 11 solvents by extended X-ray absorption fine structure (EXAFS) analysis and X-ray absorption near-edge structure (XANES). The EXAFS analyses with a one-shell model indicate that Fe2+ and Fe3+ are coordinated by six oxygen of the ligand molecules (L) and form a FeL 6-type complex in all solvents. The XANES suggests that the [FeL 6]3+ complex shows noncentrosymmetric deformation in several solvents. In protic solvents, the EXAFS analyses with a two-shell model revealed that the coordination number (n C) of the second nearest carbon around Fe3+ significantly depends on L. We interpreted the observation in terms of the distribution of the Fe-C distance.