Wesp Tobias, Bruckhoff Tim, Petry Julian, Wadepohl Hubert, Gade Lutz H
Anorganisch-Chemisches-Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Chemistry. 2022 Mar 22;28(17):e202200129. doi: 10.1002/chem.202200129. Epub 2022 Feb 28.
Ortho substituted octaazaperopyrenes (OAPPs) are a new class of functional dyes characterized by their strong electron-accepting behavior. Herein, the synthesis, as well as the electrochemical and photo physical properties of an OAPP dye, is reported. The OAPP target was prepared via selective nucleophilic substitution at the peri position of a bay chlorinated tetraazaperylene by introduction of four amino-substituents. The resulting tetraminoperylene was reacted with different acyl chlorides and anhydrides to give the twisted bay chlorinated OAPP derivatives which were isolated in their reduced dihydro-form. The OAPP target could be obtained via a palladium catalyzed dehalogenation and a subsequent oxidation. The eightfold isosteric [CH→N] replacement within the peropyrene core structure results in a large decrease of the frontier orbital energies, rendering the target compound a potent oxidant while preserving the planarity of the aromatic core. The radical anion was obtained by reduction of the OAPP with KC and characterized by EPR spectroscopy. A general discussion of the number and location of [CH→N] replacements in peropyrene structures and their frontier orbital energies is provided.
邻位取代八氮杂苝（OAPPs）是一类新型功能染料，其特点是具有很强的电子接受行为。本文报道了一种OAPP染料的合成及其电化学和光物理性质。通过在湾位氯化四氮杂苝的周位进行选择性亲核取代，引入四个氨基取代基来制备OAPP目标物。所得的四氨基苝与不同的酰氯和酸酐反应，得到扭曲的湾位氯化OAPP衍生物，这些衍生物以其还原的二氢形式被分离出来。OAPP目标物可通过钯催化的脱卤反应和随后的氧化反应获得。苝核心结构内八重等排体的[CH→N]取代导致前沿轨道能量大幅降低，使目标化合物成为一种强氧化剂，同时保持芳香核的平面性。通过用钾还原OAPP得到自由基阴离子，并通过电子顺磁共振光谱对其进行了表征。本文还对苝结构中[CH→N]取代的数量和位置及其前沿轨道能量进行了一般性讨论。
