Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
Institut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
Spectrochim Acta A Mol Biomol Spectrosc. 2021 May 15;253:119567. doi: 10.1016/j.saa.2021.119567. Epub 2021 Feb 6.
We report the development of a new spectroscopic scheme, coherent two-dimensional (2D) electronic spectroelectrochemistry. Conventional 2D electronic spectroscopy has become well established to investigate molecular energy transfer, charge transfer, or structural dynamics with femtosecond time resolution following electronic excitation, providing frequency resolution for both the excitation and the detection step. Here we combine this method with electrochemistry in a flow cell. Thus we have established access to the dynamics of various oxidized and reduced molecular species in solution. We investigate the photophysics of a tetraphenoxy-substituted perylene bisimide dye and its reduced species as a proof of principle and find substantially different dynamics for the neutral and the twofold reduced compound. The electrochemical flow cell is furthermore applied in conventional transient absorption spectroscopy and photoluminescence spectroscopies as an application in different setups.
我们报告了一种新的光谱方案，即相干二维（2D）电子光谱电化学。传统的二维电子光谱学已经得到了很好的发展，可以在电子激发后用飞秒时间分辨率研究分子能量转移、电荷转移或结构动力学，为激发和检测步骤都提供频率分辨率。在这里，我们将这种方法与电化学在流动池中结合。因此，我们已经可以访问溶液中各种氧化和还原分子物种的动力学。我们研究了四苯氧基取代的苝二酰亚胺染料及其还原物种的光物理性质，作为原理验证，并发现中性和两倍还原化合物的动力学有很大的不同。电化学流动池还可以作为不同设置中的应用，在传统的瞬态吸收光谱学和荧光光谱学中使用。
