Deciphering the working mechanism of aggregation-induced emission of tetraphenylethylene derivatives by ultrafast spectroscopy.
Deciphering the working mechanism of aggregation-induced emission of tetraphenylethylene derivatives by ultrafast spectroscopy.
复制标题
用超快光谱破译四苯乙烯衍生物聚集诱导发射的工作机制
DOI：
10.1039/c8sc01170b
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发表时间：
2018-05-28
期刊：
影响因子：
8.4
通讯作者：
Tang BZ
中科院分区：
文献类型：
--
作者：
Cai Y;Du L;Samedov K;Gu X;Qi F;Sung HHY;Patrick BO;Yan Z;Jiang X;Zhang H;Lam JWY;Williams ID;Lee Phillips D;Qin A;Tang BZ
光环化中间体的形成和准CC扭曲是AIE背后的主导过程。聚集诱导发光（AIE）是长期寻求解决聚集引起的猝灭问题的方法，该问题阻碍了荧光有机材料的有效应用。在充分理解AIE过程的工作机制的道路上，一个重要的目标是，十多年来，仍然是获得更全面的见解四苯乙烯（TPE）为基础的分子中的超快激发态动力学和AIE效应之间的相关性。在这里，我们报告了一些TPE为基础的衍生物具有不同的结构刚度和AIE性能。结合超快时间分辨光谱和计算研究，我们观察到的状态依赖的耦合运动和抑制荧光之间的直接相关性，并证明存在的光环化中间体。我们表明，占主导地位的非辐射弛豫动力学，即形成中间体或旋转周围的细长CC键，是负责的AIE效应，这是强烈的结构依赖性，但不相关的结构刚性。
Photocyclized intermediate formation and quasi CC twisting are the dominant processes behind the AIE. Aggregation-induced emission (AIE) is the long-sought solution to the problem of aggregation-caused quenching that has hampered efficient application of fluorescent organic materials. An important goal on the way to fully understand the working mechanism of the AIE process was, for more than a decade, and still remains obtaining more comprehensive insights into the correlation between the ultrafast excited-state dynamics in tetraphenylethylene (TPE)-based molecules and the AIE effect in them. Here we report a number of TPE-based derivatives with varying structural rigidities and AIE properties. Using a combination of ultrafast time-resolved spectroscopy and computational studies, we observe a direct correlation between the state-dependent coupling motions and inhibited fluorescence, and prove the existence of photocyclized intermediates in them. We demonstrate that the dominant non-radiative relaxation dynamics, i.e. formation of intermediate or rotation around the elongated CC bond, is responsible for the AIE effect, which is strongly structure-dependent but not related to structural rigidity.
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影响因子：
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作者：
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通讯作者：
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