Abstract
We have studied by absorption Mössbauer spectroscopy, some bridged derivatives of biferrocene, unoxidized (FeII– FeII) and mono-oxidized (FeII – FeIII). The mixed-valence species exhibits a quasi-delocalized behavior at the Mössbauer timescale (∼ 10−8 s), with a splitting of the lines which is interpreted in terms of a partial valence trapping. This in turn reveals intramolecular properties at variance from those of the unbridged cation. SCC-Xα MO calculations have been performed; they correctly reproduce the measured quadruple splittings and provide evidence that the HOMO of the mixed-valence complex is of\(d_{xy} ,d_{x^2 - y^2 } \) type. Some consequences on the mixed-valence properties are discussed.
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Rabah, H., Guillin, J., Cereze-Ducouret, A. et al. Mössbauer study and molecular orbital calculations on some bimetallic derivatives of ferrocene and ferricinium. Hyperfine Interact 77, 51–66 (1993). https://doi.org/10.1007/BF02320298
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DOI: https://doi.org/10.1007/BF02320298