Theoretical investigation on remote-control photocycloreversion of dithienylethene driven by azobenzene chromophores

Abstract

When adding two azobenzene chromophores on a dithienylethene molecule, the irradiation at 450 nm can effectively arouse the cycloreversion reaction of the ring-closed dithienylethene. We investigated the frontier molecular orbitals and absorption properties of such series of molecules and inferred the mechanism of the ring-opening reaction. The 450 nm light sensed by the side azobenzene groups can excite the whole molecule to a high excited state, and through electronic transition and energy transfer the active electron may centre on the dithienylethene ring part, then the ring-opening happens. While for the ring-open form, the energy of the 450 nm light is not high enough to promote the electron to the exact molecular orbital occupying the central dithienylethene ring, so it cannot cause the ring-closing reaction.

Keywords: Absorption spectra; Azobenzene; Dithienylethene; Photocycloreversion; Remote-control; TD-DFT.