Abstract
Ligand-field spectra of tetrahedral CoX 2−4 and octahedral Cr(NCS) 3−6 were measured in a number of solvents. Care was taken to ensure complete formation of the anionic species to be investigated. Considerable variations in intensity were found for complexes with highly polarizable ligands. For Co(NCS) 2−4 the oscillator strength of the4T1(P) transition in aqueous solution was only about 1/5 that in a number of organic solvents, with little variation in these solvents. For Cr(NCS) 3−6 the intensities are highest in aqueous solution, and some variation is observed for the nonaqueous solvents. These data for the chromium complex correlate at least qualitatively with variations of the excited state lifetimes in these solvents. Nonlinear changes of intensities in solvent mixtures can be taken as an indication of preferential solvation of the anionic complex by nonaqueous solvent molecules. The reported results are a strong indication of large differences in solvent/solute interactions between water and the nonaqueous solvents.
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Aust, H., Lehmann, G. Solvent effects on ligand-field intensities in some anionic complexes of 3d ions. J Solution Chem 6, 443–453 (1977). https://doi.org/10.1007/BF00645838
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DOI: https://doi.org/10.1007/BF00645838