取代硫代蒽酮的光物理和光反应性

M. Neumann, M. Gehlen, M. Encinas, N. Allen, T. Corrales, C. Peinado, F. Catalina
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引用次数: 67

摘要

本文研究了取代噻唑酮的光物理性质和激发态的相互作用,以预测它们在光聚合体系中作为光引发剂的行为。硫杂蒽酮环上2位的电子给体基团具有较高的荧光量子产率、发射光谱的红移和较长的单重态寿命,这是由于芳香体系中较高的电子密度导致了nπ*和ππ*激发态的分离。对于某些衍生物,由于溶剂的缓慢弛豫,已观察到双指数衰减。胺对单线态猝灭的速率常数接近扩散极限,不受取代基的修饰。另一方面,噻唑酮环上2位电子给体基团的取代降低了对胺和烯烃的三联体反应性。在化合物侧链上加入双键不影响硫代蒽酮的寿命和反应性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Photophysics and photoreactivity of substituted thioxanthones
The photophysics and the interaction of the excited states of substituted thioxanthones have been studied in order to be able to predict their behaviour as photoinitiators in photopolymerization systems. Electron-donor groups in position 2 in the thioxanthone ring lead to high fluorescence quantum yields, red-shifts in the emission spectra and long singlet lifetimes, explained by the separation of the nπ* and ππ* excited states induced by the higher electron density of the aromatic system. For some of the derivatives a biexponential decay due to slow relaxation of the solvent has been observed. Rate constants for the quenching of the singlet state by amines are near the diffusional limit and are not modified by substituents. On the other hand, substitution of electron-donor groups on the thioxanthone ring in position 2 decreases the triplet reactivity towards amines and alkenes. The incorporation of double bonds on the side chains of the compounds does not affect the lifetimes and reactivity of the thioxanthones.
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