Construction of Structurally Rigid Azulen-6-ones via Migratory Rearrangement of Spirocycles and Their Photophysical Studies.

We report the synthesis of polysubstituted 1,1,2,3-tetraarylazulen-6-ones through the ring opening and scaffold rearrangement of spirocycles in the presence of ferric chloride under ambient conditions. Control experiments shown that this reaction may proceeded through a radical cation mechanism and futher theoretical calculation revealed that the electronic distribution of the radical cation intermediate dominated this oxidative rearrangement instead of dehydrogenation. It is noteworthy that some interesting photophysical properties, including aggregation-induced emission, halochromism, and two-photon fluorescence, were discovered for the azulen-6-one 2a, making them to work as promising functional materials in optical-related fields.