Structure–function relationships of donor–acceptor Stenhouse adduct photochromic switches

Abstract

The first in-depth, systematic study of the photoswitching properties of Donor–Acceptor Stenhouse Adducts (DASAs) is reported. Barbituric acid derived DASAs functionalised with 14 different amines ranging from dimethylamine to 4-methoxy-N-methylaniline were structurally characterised in solution using ¹H and ¹³C NMR spectroscopy and, in eight cases, in the solid state by single crystal X-ray diffraction. The distribution of coloured and colourless isomers in the dark, their photostationary states under irradiation, apparent thermal half-lives, and fatigue resistance are systematically compared. A simple kinetic model is used to characterise photoswitching behaviour and reveals that minor structural modifications can significantly improve the photoswitching properties of DASA photochromes. These modifications result in excellent photoswitching properties for ‘1^st generation’ DASAs in chloroform, including exceptional fatigue resistance, opening the door for these photochromic molecules to find widespread applications.