Effect of solvents on the barrierless reaction in the excited state of cyanine dye |
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Authors: | Email author" target="_blank">Juan?FengEmail author Junfeng?Xiang Huijuan?Zhang Xicheng?Ai Jianping?Zhang Xingkang?Zhang Guangzhi?Xu |
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Institution: | (1) State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Center for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, 100080 Beijing, China;(2) Technique Institute of Physics and Chemistry, Chinese Academy of Sciences, 100080 Beijng, China |
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Abstract: | UV-Vis, fluorescence spectroscopy and time resolved spectroscopic technique on picosecond and femto- second scales have been utilized to investigate the effect of steric hindrance and multiple hydroxyl groups of solvents on the barrierless isomerization in excited state of 3, 3′- di(3-sulfopropyl)thiacyanine triethylaminium salt. The results show that the factors mentioned above may be responsible for a different "short-time behavior" of the bleaching signal on the ground state and nonlinear viscosity dependence of the excited-state lifetime in isopropanol and glycol. These phenomena are distinguished from the situation reported in the long-chained monohydroxyl alcohol solvents. However, the dye molecule still exhibits the analyzing- wavelength dependence of the observed fluorescence lifetime, that is, the fluorescence lifetime increases with the increasing of analyzing-wavelength. The conclusions are in agreement with those drawn from femtosecond upconversion fluorescence experiments and further exemplify the barrierless isomerization model in the excited state. |
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Keywords: | picosecond time-resolved fluorescence spectroscopy femtosecond transient absorption technique barrierless isomeriza-tion |
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