苯乙烯
光化学
量子产额
烯烃
化学
反应速率常数
蒽
猝灭(荧光)
激发态
单重态
单线态氧
双键
聚合
荧光
产量(工程)
材料科学
氧气
高分子化学
共聚物
有机化学
动力学
聚合物
催化作用
物理
量子力学
核物理学
冶金
作者
H.-J. Timpe,Steffen Neuenfeld
摘要
Some heteroatom-containing anthracene dyes are bleached out in a reductive pathway with quantum yields, Φb, between 10–2 and 10–4 by excitation at their long-wavelength maximum in methanol solutions containing styrene (5 mol dm–3). The photoreduction of the dye safranine T by styrene has been investigated. The excited safranine T singlet undergoes and electron-transfer reaction with a rate constant of ksq= 5 × 107 dm3 mol–1 s–1 and an overall efficiency of ηel= 0.019. Three different experimental procedures (fluorescence quenching, triplet-state yield measurement, Φb measurement) give the same value within the experimental limits. As determined by means of short-time techniques, the excited triplet state does not interact with the alkene. In the presence of oxygen, there is an additional oxidative pathway, involving the primary products of the photoreduction process. The Φb values are dependent on the solvent used. A correlation with Gutmann's donor numbers, DN, has been obtained (–log Φb= 0.030DN + 1.9). The semireduced safranine T species are able to add onto the styrene double bond with a rate constant of krm= 6 × 103 dm3 mol–1 s–1 giving rise to initiation of free radical polymerization of this alkene.
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