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Photochemical Origin of the Darkening of Copper Acetate and Resinate Pigments in Historical Paintings.

Copper acetate and copper resinate pigments are bimetallic CuII complexes in which metal atoms are bridged by four carboxylate ligands (acetate or abietate). Prepared with lindseed oil as binder, these green pigments were particularly used in easel paintings between the 15th and 17th centuries. Unfortunately, they had the tendency to darken in an irreversible way, explaining why they fell into disuse. The darkening mechanism of films of copper pigments in linseed oil is studied by electron paramagnetic resonance (EPR) and by optical absorption spectroscopy (OAS). EPR and OAS reveal different chemical and photochemical behaviors depending on the type of copper complex and on the binding oil. The effect of light is investigated by illuminating the films at ∼410 nm in the bridging ligand-to-metal charge transfer (LMCT) transition. The photodarkening manifests itself as the appearance of an optical absorption band around 22 000 cm-1 and a decrease of the EPR intensity of bimetallic copper complexes. These effects are explained by the photoinduced substitution of acetate (or abietate) bridging ligands by dioxygen molecules from ambient atmosphere. The resulting peroxo-CuII dimer is characterized by a red shift of the LMCT and an increase of the exchange interaction in the ground state, which is responsible for the decrease of the EPR intensity due to the depletion of the paramagnetic S = 1 state. This mechanism explains the differences in darkening intensity observed with different pigment compositions (resinate versus acetate, raw linseed oil versus boiled linseed oil).