Ring closure dynamics of BTE-based photochromic switches: Perfluoro- versus perhydrocyclopentene derivatives

The switching behavior of 1,2-bis(5-phenyl-2-methylthien-3-yl)perfluorocyclopentene and its nonfluorinated (perhydro) analogue are compared. For both molecules, the dynamics after optical excitation can be separated into three regimes: preswiching due to excited state mixing; the ring closure itself; postswitching related to vibrational cooling. The fluorinated version switches faster than its nonfluorinated analogue by about a factor of 4.7. This is explained by electronic level shifts near the crossing region between the S-1 and S-0 potential energy surfaces. In the nonfluorinated molecule the various levels involved in the switching have well-separated transition frequencies, which allow for a clear interpretation of experimental data. Thus, the fluorinated molecule makes a better (more efficient and faster) switch, but the nonfluorinated molecule provides a better model system for fundamental studies.