Structure–Optical Properties Relationships in Cobalt-Based Purple Pigments Used by Robert Delaunay

Following the industrial revolution and the modernization of chemistry, purple became one of the most popular colors in the palettes of late 19th- to 20th-century painters. Among them, Robert Delaunay (1885-1941) was one of the key artists of the avant-garde movement in France in the early 20th century. Although widely used in modern and contemporary paintings, inorganic purple pigments of the cobalt phosphate and cobalt arsenate families have been little studied chemically until now. The diversity of emerging chemical syntheses resulted in a wide range of products, characterized by a high diversity of hues, function of their respective composition, and crystal structures. The present work combines structural and optical analyses to probe the purple pigments used by Delaunay. Reference materials synthesized in the laboratory were characterized via synchrotron radiation-based high-angular-resolution X-ray powder diffraction and UV-vis-NIR spectroscopy. Structure-color relationships were established for the first time for several inorganic compounds of the Co-P/As family. Two of Robert Delaunay’s earliest masterpieces conserved at the Centre Pompidou in Paris were probed in situ via X-ray powder diffraction in imaging mode and fiber optic UV-vis-NIR reflectance spectroscopy. The results highlight the decisive effect of their structural chemistry on the palettes of modern and contemporary painters.