Exposing the inadequacy of redox formalisms by resolving redox inequivalence within isovalent clusters.

ABSTRACT: In this report we examine a family of trinuclear iron complexes by multiple-wavelength, anomalous diffraction (MAD) to explore the redox load distribution within cluster materials by the free refinement of atomic scattering factors. Several effects were explored that can impact atomic scattering factors within clusters, including 1) metal atom primary coordination sphere, 2) M-M bonding, and 3) redox delocalization in formally mixed-valent species. Complexes were investigated which vary from highly symmetric to fully asymmetric by ⁵⁷Fe Mössbauer and X-ray diffraction to explore the relationship between MAD-derived data and the data available from these widely used characterization techniques. The compounds examined include the all-ferrous clusters [ ⁿ Bu_4<

SUBMITTER: Bartholomew AK 

PROVIDER: S-EPMC6690028 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature