Markovic Aleksandra, Buschbeck Leon, Klüner Thorsten, Christoffers Jens, Wittstock Gunther
Carl von Ossietzky University Oldenburg School of Mathematics and Science, Chemistry Department D-26111 Oldenburg Germany.
ChemistryOpen. 2019 Jul 2;8(9):1176-1182. doi: 10.1002/open.201900138. eCollection 2019 Sep.
Derivatives of 2,5-diaminoterephthalate (DAT) are efficient fluorescence dyes that are also redox-active, thus allowing for the electrochemical manipulation of spectral properties. The electrochemical behaviour of seven DAT derivatives was studied by cyclic voltammetry in dichloromethane. In the absence of a proton donor, DATs should be oxidized in two one-electron steps. The first step is usually quasi-reversible while the second step is either quasi-reversible or irreversible. Some electrochemical properties such as the formal potentials and the ratio between the anodic and the cathodic current were determined from the cyclic voltammograms. Correlation between the formal potential of first oxidation and the absorption or the fluorescence emission wavelengths are established for this specific type of dyes. These correlations were confirmed with density functional theory calculations.
2,5-二氨基对苯二甲酸酯（DAT）的衍生物是高效荧光染料，同时也是氧化还原活性的，因此可以对光谱特性进行电化学操纵。通过循环伏安法在二氯甲烷中研究了七种DAT衍生物的电化学行为。在没有质子供体的情况下，DATs应通过两个单电子步骤被氧化。第一步通常是准可逆的，而第二步要么是准可逆的，要么是不可逆的。从循环伏安图中确定了一些电化学性质，如形式电位以及阳极和阴极电流之比。针对这种特定类型的染料，建立了第一次氧化的形式电位与吸收或荧光发射波长之间的相关性。这些相关性通过密度泛函理论计算得到了证实。
