Solid state photochromism and thermochromism of two related N-salicylidene anilines

The crystalline structure and optical properties of N-salicylidene-p-cyanoaniline and N-salicylidene-p-carboxyaniline were investigated in solid state (microcrystalline powder), with the purpose to connect the effects of substitution and crystal packing with their optical properties. Diffuse reflectance and fluorescence spectroscopy were used to study the absorption and emission properties upon photoirradiation and cooling down to the liquid nitrogen temperature. The Stokes-shifted fluorescence, with a quantum yield of about 10−2–10−1, is given by the tautomeric cis-keto species formed as a result of the excited state intramolecular proton transfer from the initial enol structure. Despite their similar geometrical parameters, only SA-COOH is photochromic, which is in contradiction with literature. On the other side, the thermochromism is especially strong at SA-CN. The study shows the behavior of SA-CN similar to that of a classical anil, while SA-COOH presents interesting features that contradict the presumed behavior based only on its supramolecular structure.