Abstract
Cobalt and chromium K-edge XAFS (X-ray Absorption Fine Structure) spectra of [Co(ox) 3[ 3−, [Co(ox) 2] −, [Co(mal) 2en] − and [Cr(ox) 3] 3− (ox = oxalate, mal = malonate, en = ethylenediamine) in solids and in various solvents were measured. XANES (X-ray Absorption Near-Edge-Structure) spectra of a trisoxolato cobalt complex, and a chromium complex, vary with the type of solvent, while such a solvent effect was not detected for [Co(ox) 2en] − and [Co(mal) 2en] −. EXAFS (Extended X-ray Absorption Fine Structure) analyses of the trisoxalato complexes in solvents indicate that metal-coordinating atom distances vary depending on the solvents used and linear reduction of the distances was observed with increasing Gutmann's acceptor number of a solvent. This trend is apparently in accord with the observed blue shifts in d-d absorption spectra of [Co(ox) 3] − in greater acceptor number solvents. Furthermore, it was found that othr metal-ligand atom distances than interatomic distances of metal-directly coordinating atoms also shrink with acceptor numbers of solvents.
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