Universität Würzburg, Institut für Organische Chemie, Am Hubland, 97074, Würzburg, Germany.
Universität Würzburg, Center for Nanosystems Chemistry (CNC), Theodori-Boveri-Weg, 97074, Würzburg, Germany.
Chemistry. 2018 Jul 2;24(37):9409-9416. doi: 10.1002/chem.201801191. Epub 2018 Jun 5.
Herein we report a palladium-catalyzed annulation reaction consisting of a Suzuki-Miyaura cross-coupling and a C-H arylation cascade for the synthesis of tetrachlorinated polycyclic aromatic dicarboximides (PADIs). This convergent synthetic route afforded a broad series of hitherto unknown electron-deficient PADIs under optimized reaction conditions by coupling of a dibromo-tetrachloro-perylene dicarboximide with different polycyclic aromatic hydrocarbon (PAH) boronic acid pinacol esters in up to 89 % yields. The new PADI compounds show broad absorption in the visible range and some of them emit in the near-infrared (NIR) region. Cyclic and square wave voltammetric studies revealed that these tetrachlorinated PADIs are more electron-deficient than a non-chlorinated reference compound and they possess lower lying frontier orbitals. Thus, the newly synthesized electron-poor PADIs are potential n-type semiconductors. Moreover, these chlorinated PADIs are interesting building blocks for the construction of large π-extended arrays by metal-mediated coupling reactions.
在此，我们报告了一种钯催化的环化反应，包括 Suzuki-Miyaura 交叉偶联和 C-H 芳基化级联反应，用于合成四氯代多环芳烃二酰亚胺（PADIs）。在优化的反应条件下，通过二溴四氯对苯二甲酰亚胺与不同多环芳烃（PAH）硼酸频哪醇酯的偶联，该收敛合成路线以高达 89%的收率提供了广泛的 hitherto 未知的缺电子 PADIs。新的 PADI 化合物在可见光范围内具有广泛的吸收，其中一些在近红外（NIR）区域发射。循环伏安法和方波伏安法研究表明，这些四氯代 PADIs 比非氯代参比化合物更缺电子，并且具有更低的前沿轨道。因此，新合成的缺电子 PADIs 是潜在的 n 型半导体。此外，这些氯化 PADIs 是通过金属介导的偶联反应构建大 π 扩展阵列的有趣构建块。
