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Effect of solvents on the barrierless reaction in the excited state of cyanine dye

机译：溶剂对花青染料激发态无阻反应的影响

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UV-Vis, fluorescence spectroscopy and time resolved spectroscopic technique on picosecond and femtosecond 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.
机译：皮秒和飞秒级别的紫外可见，荧光光谱和时间分辨光谱技术已被用于研究空间位阻和溶剂中的多个羟基对3，3'-二（3-磺丙基）激发态下无障碍异构化的影响硫氰酸三乙ami盐结果表明，上述因素可能是造成漂白信号在基态上的不同“短时行为”以及异丙醇和乙二醇中激发态寿命的非线性粘度依赖性的原因。这些现象不同于在长链一羟基醇溶剂中报道的情况。然而，染料分子仍然表现出所观察到的荧光寿命的分析波长依赖性，即，荧光寿命随着分析波长的增加而增加。这些结论与飞秒上转换荧光实验得出的结论一致，并进一步例证了激发态的无障碍异构化模型。

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