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 S1 and S0 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.