Copper Soaps Formation in Verdigris–Linseed Oil Painting Mixtures: A Multispectroscopic Characterization

Copper acetate (also known as verdigris) is a bimetallic Cu(II) greenish pigment widely used in oil paintings. Since ancient times, this pigment has been known as a degradation-prone compound, especially when combined with lipidic binders. However, the degradation mechanism and the involved species have not yet been disclosed. In this article, we study verdigris interactions with linseed oil in painting mock-ups, stressing out the formation of copper-based complexes and proposing reaction routes. Such complex systems are studied by applying a complementary multispectroscopic approach: a combination of continuous-wave (CW) electron paramagnetic resonance (EPR), electron spin echo envelope modulation (ESEEM), and Raman and attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopies. Based on the experimental evidence, we propose the following mechanism: the neutral copper acetate shifts to a basic verdigris-promoting triglyceride hydrolysis, aided by the coordination of Cu(II) cations toward the carboxylic functions. The increased amount of free fatty acids in the mixtures triggers the formation of monomeric Cu(II) complexes. Afterward, the oil polymerization reaction occurs, and secondary oxidation species, containing OH groups in the alkyl chain, act as further ligands for copper nuclei. This is the first time, to the best of our knowledge, that a comprehensive view is proposed.