Abstract
The photo-reduction of a series of cobalt(III) complexes of the type cis-β-[Co(trien)(4-R-Py)Cl]Cl 2 where trien=triethylenetetraamine and R = H, Me, Et, t-Bu, COMe, and CN has been studied in water/propan-2-ol and water/1,4-dioxane media of varying compositions. The photo-reduction quantum yield (Φ Co(II)) data were correlated with solvent and structural parameters with an aim to shed some light on the mechanism of the reaction. Correlation of Φ Co(II) with macroscopic solvent parameters viz. relative permittivity indicates that the reactivity is influenced by both specific and non-specific solute–solvent interactions. Kamlet–Taft solvatochromic comparison method was used to separate and quantify these effects. The observed non-linear concave downwards type Hammett plot is explained by assuming shift in the excited state within the same overall reaction pathway.
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