Charge and Spin-State Characterization of Cobalt Bis(o-dioxolene) Valence Tautomers Using Co Kß X-ray Emission and L-Edge X-ray Absorption Spectroscopies.

The valence tautomeric states of Co(phen)(3,5-DBQ)2 and Co(tmeda)(3,5-DBQ)2, where 3,5-DBQ is either the semiquinone (SQ-) or catecholate (Cat2-) form of 3,5-di-tert-butyl-1,2-benzoquinone, have been examined by a series of cobalt-specific X-ray spectroscopies. In this work, we have utilized the sensitivity of 1s3p X-ray emission spectroscopy (Kß XES) to the oxidation and spin states of 3d transition-metal ions to determine the cobalt-specific electronic structure of valence tautomers. A comparison of their Kß XES spectra with the spectra of cobalt coordination complexes with known oxidation and spin states demonstrates that the low-temperature valence tautomer can be described as a low-spin CoIII configuration and the high-temperature valence tautomer as a high-spin CoII configuration. This conclusion is further supported by Co L-edge X-ray absorption spectroscopy (L-edge XAS) of the high-temperature valence tautomers and ligand-field atomic-multiplet calculations of the Kß XES and L-edge XAS spectra. The nature and strength of the magnetic exchange interaction between the cobalt center and SQ- in cobalt valence tautomers is discussed in view of the effective spin at the Co site from Kß XES and the molecular spin moment from magnetic susceptibility measurements.