A dominant factor of the cycloreversion reactivity of diarylethene derivatives as revealed by femtosecond time-resolved absorption spectroscopy.

Dynamics of the cycloreversion reaction of a photochromic diarylethene derivative with a small ring-opening reaction yield (∼1%) was investigated by using femtosecond transient absorption spectroscopy. The reaction rate constant and activation barrier on the reaction coordinate were quantitatively analyzed on the basis of the temperature and excitation wavelength dependencies of the reaction yield and excited state dynamics. From the comparison of the present results with those in a more reactive derivative, we concluded that a key factor regulating the overall reaction yield is the branching ratio at the conical intersection where the excited state population is split into the product and the initial reactant. The excitation wavelength dependence of the dynamics indicated that the geometrical relaxation and vibrational cooling proceed in a few picosecond time scale behind the cycloreversion process, and the vibrational excess energy assists the molecule to climb up the energy barrier.