Electroabsorption of dimers containing MM (M = Mo, W) quadruply bonded units: Insights into the electronic structure of neutral coupled redox centers and their relationship with mixed valence ions

Malcolm H. Chisholm, Benjamin J. Lear, Alberto Moscatelli, Linda A. Peteanu

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

The electroabsorption spectra for the metal-to-ligand charge transfer transition in complexes containing oxalate and terephthalate bridged MM quadruply bonded units, [(MM)(pivalate)3]2- μ2-BR, where M = Mo or W and BR = oxalate or terephthalate, are reported. The measured magnitude of the change in dipole moment (|Δμ|) and the change in polarizability (Δ∝) that accompany this electronic transition are found to be small and not to follow the behavior expected on the basis of the two-state model. In addition, the trend in the value of Δ∝ for the neutral states is mirrored by the trend in the degree of electronic coupling (HAB) for the strongly coupled mixed valence states formed by the same complexes in their singly oxidized states.

Original languageEnglish (US)
Pages (from-to)3706-3713
Number of pages8
JournalInorganic chemistry
Volume49
Issue number8
DOIs
StatePublished - Apr 19 2010

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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