Decisive Factors in the Photoisomerization Behavior of Crowned Spirobenzopyrans: Metal Ion Interaction with Crown Ether and Phenolate Anion Moieties

Abstract

The influence of metal ion interaction with crowned spirobenzopyrans on the photoisomerization behavior was investigated through the use of various solvents, crowned spirobenzopyrans, and metal ions. Studies on the photoisomerization behavior of crowned spirobenzopyrans in various solvents revealed that solvation of the phenolate anion moiety in the merocyanine form induced photoisomerization back to the spiropyran form, giving rise to negative photochromism. Metal ion interaction with the phenolate anion moiety similarly caused photoisomerization back to the spiropyran form, while that with the crown ether moiety just produced a polar environment and its influence on photoisomerization behavior was dependent on the affinity of the metal ion captured by the crown ether moiety for the phenolate anion. Therefore, photochromic switching of crowned spirobenzopyrans between positive and negative to control the metal ion interaction with the phenolate anion moiety through the crown ether moiety is possible. This finding suggests a molecular design method for crowned spirobenzopyrans showing desired ion-responsive photochromism.