Tunable Visible and Near Infrared Photoswitches

James R. Hemmer, Saemi O. Poelma, Nicolas Treat, Zachariah A. Page, Neil D. Dolinski, Yvonne J. Diaz, Warren Tomlinson, Kyle D. Clark, Joseph P. Hooper, Craig Hawker, and Javier Read de Alaniz
J. Am. Chem. Soc.
2016
138, 13960−13966

A class of tunable visible and near-infrared donor−acceptor Stenhouse adduct (DASA) photoswitches were efficiently synthesized in two to four steps from commercially available starting materials with minimal purification. Using either Meldrum’s or barbituric acid “acceptors” in combination with aniline-based “donors”, an absorption range spanning from 450 to 750 nm is obtained. Additionally, photoisomerization results in complete decoloration for all adducts, yielding fully transparent, colorless solutions and films. Detailed investigations using density functional theory, nuclear magnetic resonance, and visible absorption spectroscopies provide valuable insight into the unique structure−property relationships for this novel class of photoswitches. As a final demonstration, selective photochromism is accomplished in a variety of solvents and polymer matrices, a significant advantage for applications of this new generation of DASAs.