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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >On the Evidence Obtained by Exciting 7-Azaindole at 320 nm in 10~(-2) M Solutions
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On the Evidence Obtained by Exciting 7-Azaindole at 320 nm in 10~(-2) M Solutions

机译:在10〜(-2)M溶液中激发7-氮杂吲哚在320 nm处获得的证据

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摘要

Careful analysis of the UV absorption spectra for 2 * 10~(-2) M solutions of 7-azaindole (7AI) in 3-methylpentane and n-hexane revealed that the onset of the first absorption band lies at ca. 335 nm, i.e., it is bathochromically shifted by 15 nm with respect to the onset of the band for the doubly-H-bonded dimer (D), so an additional aggregate species must exist in solution. Interestingly,this new species, like the double-H-bonded dimer, also emits in the region around 480 nm. The corresponding fluorescence excitation spectra confirm that the onset of the excitation lies between 335 and 340 nm. The presence of two different molecular structures in the red edge of the first absorption band, which undergo a proton transfer reaction on photoexcitation, seriously questions the model of Zewail et al. that because of two kinetic rates measured and ascribed to protontransfer processes, the biprotonic transfer on photoexcitation in a 2 * 10~(-2) M solution of 7AI excited at 320 nm is a nonconcerted mechanism.
机译:仔细分析7-氮杂吲哚(7AI)在3-甲基戊烷和正己烷中的2 * 10〜(-2)M溶液的UV吸收光谱,发现第一个吸收带的起始点位于。 335 nm,即相对于双H键合的二聚体(D)的谱带的开始,其发生了红移(chromochromically)偏移15 nm,因此溶液中必须存在其他聚集体。有趣的是,这种新物种,如双H键合的二聚体,也在480 nm附近发射。相应的荧光激发光谱证实了激发的起点在335和340 nm之间。在第一个吸收带的红色边缘存在两个不同的分子结构,这些结构在光激发下会发生质子转移反应,这严重质疑了Zewail等人的模型。由于测量和归因于质子转移过程的两个动力学速率,在320 nm激发的2Al的2 * 10〜(-2)M溶液中光激发时的双质子转移是一个未经证实的机制。

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