Controlled Excited-State Dynamics and Enhanced Fluorescence Property of Tetrasulfone[9]helicene by a Simple Synthetic Process
Controlled Excited-State Dynamics and Enhanced Fluorescence Property of Tetrasulfone[9]helicene by a Simple Synthetic Process
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DOI：
10.1021/acs.jpcc.6b01123
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发表时间：
2016-03
影响因子：
3.7
通讯作者：
Yuki Yamamoto;Hayato Sakai;J. Yuasa;Y. Araki;T. Wada;T. Sakanoue;T. Takenobu;T. Kawai;Taku Hasobe
中科院分区：
文献类型：
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作者：
Yuki Yamamoto;Hayato Sakai;J. Yuasa;Y. Araki;T. Wada;T. Sakanoue;T. Takenobu;T. Kawai;Taku Hasobe
通过四硫杂[9]螺烯（PTTH）的一步氧化反应合成了四砜[9]螺烯（PTSH），并对其荧光性质和激发态动力学进行了研究。在电化学测量中，PTSH的还原电位在正方向上移动了约1.0 V，因为它的电子接受砜单元相比，PTTH。电化学测量的结果与密度泛函理论（DFT）方法和稳态光谱测量计算的能级一致。此外，实现了绝对荧光量子产率（ΦFL）的显著增强。PTSH的绝对荧光量子产率达到0.27，约为PTTH（ΦFL = 0.03）的10倍。这种增强的ΦFL可以成功地解释了相应的动力学比较。其原因主要是最低单重态（S1）和三重态（T1）激发态之间的能隙ΔEST增大。
Tetrasulfone[9]helicene (PTSH) was newly synthesized to improve and evaluate its fluorescence and excited-state dynamics through a single-step oxidation reaction of tetrathia[9]helicene (PTTH). In electrochemical measurements, the reduction potential of PTSH was shifted in a positive direction by approximately 1.0 V when compared to that of PTTH because of its electron-accepting sulfone units. The results of the electrochemical measurements agree with the energy levels calculated by density functional theory (DFT) methods and steady-state spectroscopic measurements. Furthermore, a significant enhancement of the absolute fluorescence quantum yield (ΦFL) was achieved. The absolute fluorescence quantum yield of PTSH attained 0.27, which is approximately 10 times larger than that of PTTH (ΦFL = 0.03). Such an enhancement of ΦFL can be successfully explained by the corresponding kinetic comparison. The reason is mainly the increased energy gap ΔEST between the lowest singlet (S1) and triplet (T1) excited state...