학술논문
A dominant factor of the cycloreversion reactivity of diarylethene derivatives as revealed by femtosecond time-resolved absorption spectroscopy.
Document Type
Academic Journal
Author
Sotome H; Division of Frontier Materials Science and Center for Advanced Interdisciplinary Research, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.; Une K; Division of Frontier Materials Science and Center for Advanced Interdisciplinary Research, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.; Nagasaka T; Division of Frontier Materials Science and Center for Advanced Interdisciplinary Research, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.; Kobatake S; Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, Sumiyoshi, Osaka 558-8585, Japan.; Irie M; Department of Chemistry and Research Center for Smart Molecules, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501, Japan.; Miyasaka H; Division of Frontier Materials Science and Center for Advanced Interdisciplinary Research, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.
Source
Publisher: American Institute of Physics Country of Publication: United States NLM ID: 0375360 Publication Model: Print Cited Medium: Internet ISSN: 1089-7690 (Electronic) Linking ISSN: 00219606 NLM ISO Abbreviation: J Chem Phys Subsets: PubMed not MEDLINE; MEDLINE
Subject
Language
English
Abstract
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.