Beyond the color: A structural insight to eosin-based lakes

Motivated by the fugitive and undisclosed nature of eosin-derived pigments as used by Vincent van Gogh, this paper presents the syntheses of monometallic and historical bimetallic eosin-based lakes and structural elucidation by MS, ATR-FTIR and NMR. Specifically two monometallic (Al, Pb) and several bimetallic lakes (on varying Al and Pb constituents) have been synthesized and examined alongside two reference compounds: eosin disodium salt and eosin Y. Resulting monometallic lake complexes are 2:1 adducts (dye:metal) with the carboxylic group coordinating the metal. In historical lake preparations, no correlation between the coordinating metals and the resulting lake color can be made. On production and investigations of different eosin lake substrates, two main anchored species have been distinguished: H-bonded for eosin onto Pb-substrates and a further bridged bidentate for eosin onto alumina. A prominent tendency to form 2:1 eosin:Pb adducts emerged in each Pb-containing recipe. Evidence concerning historical lakes suggests that eosin can diversely coordinate to metals thus producing a variety of nuances in according to experimental pH and reaction conditions. This behavior may well explain observed discrepancies between historical recipes and experimental findings regarding the coordination of eosin to one or more metals. (C)2017 Elsevier Ltd. All rights reserved.