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Sensitization mechanisms from excited‐singlet state of pyrromethene dye to a radical‐generating reagent in a poly(methylmethacrylate) film
Author(s) -
Urano Toshiyuki,
Ito Hideki,
Yamaoka Tsuguo
Publication year - 1999
Publication title -
polymers for advanced technologies
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.61
H-Index - 90
eISSN - 1099-1581
pISSN - 1042-7147
DOI - 10.1002/(sici)1099-1581(199906)10:6<321::aid-pat881>3.0.co;2-c
Subject(s) - materials science , excited state , fluorescence , photochemistry , quenching (fluorescence) , analytical chemistry (journal) , singlet state , flash photolysis , chemistry , optics , atomic physics , physics , reaction rate constant , organic chemistry , kinetics , quantum mechanics
The sensitization mechanisms of a pyrromethene dye with a radical‐generating reagent, 3,5,3′,5′‐tetramethylpyrromethene‐BF 2 (BH) with 3,3′,4,4′‐tetrakis(t‐butyldioxycarbonyl)benzophenone (BP), in a poly‐ (methylmethacrylate) (PMMA) film were investigated by laser flash phoptolysis using a total reflection cell and single photon counting. From the laser flash photolysis, strong fluorescence was detected though no transient absorption was detected. The fluorescence intensity was significantly decreased with increasing concentration of BP, apparently exhibiting Perrin‐type static quenching at a quenching radius, R f = 26 Å. From the examination of decay profile using single photon counting, logarithmic plots of fluorescence decay in a PMMA film afforded a nonlinear, convex reduction, corresponding to a streched exponential decay, while the logarithmic plots in acetonitrile showed a linear relationship. With increasing concentration of BH, the fluorescence maximum was shifted to red, and the intensity of fluorescence was significantly reduced. The red shift of fluorescence, the nonlinear fluorescence logarithmic decay and the large reduction in fluorescence indicate a dispersive photoexcited state and a relaxation of excitation energy hopping across an array of sites with Gaussian energy distribution. Moreover, after incorporating BP, the convex logarithmic plots became more steep, and the fluorescence maximum was also shifted to red, exhibiting a nonstatic quenching process competitive to the excitation energy hopping. Thus the sensitization of photoinitiator system containing BH and BP, whose contents were almost same as that in the commercial products, was due to a static quenching process from dispersive singlet excited BH to BP ground state, and the nonstatic quenching process competitive to the excitation energy hopping was minimal. Copyright © 1999 John Wiley & Sons, Ltd.