Jiang Wenlin, Liu Zitong, Zhu Danlei, Zheng Wenyu, Chen Liangliang, Zhang Xisha, Zhang Guanxin, Yi Yuanping, Jiang Lang, Zhang Deqing
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory for Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2021 May 3;60(19):10700-10708. doi: 10.1002/anie.202102131. Epub 2021 Mar 23.
Diketopyrrolopyrrole (DPP) as a building block has been intensively investigated for organic semiconductors and light emitting materials. The synthesis of N-aryl DPPs remains challenging. Herein, we firstly report a new easily handled synthetic method toward N-aryl DPPs through H-DPP with diaryliodonium salt in the presence of CuI, which shows broad reaction scope. Sixteen N-aryl DPPs, including phenyl, furan and thiophene as flanking aromatic groups, were synthesized with yields up to 78 %. These N-aryl DPPs are fluorescent in both solutions and solid states, with quantum yields up to 96 % and 40 %, respectively. Moreover, we show that the reaction between H-DPP and diaryliodonium salt can lead to π-expanded DPPs by using Pd(OAc) as catalyst. Nine π-expanded DPPs were obtained in 27-61 % yields. These π-expanded DPPs exhibit good semiconducting properties with hole mobility of 0.71 cm V s , demonstrating that they are useful building blocks for high performance organic semiconductors.
作为一种结构单元，二酮吡咯并吡咯（DPP）已被广泛研究用于有机半导体和发光材料。N-芳基二酮吡咯并吡咯（N-aryl DPPs）的合成仍然具有挑战性。在此，我们首次报道了一种在碘化亚铜（CuI）存在下，通过H-DPP与二芳基碘鎓盐制备N-芳基二酮吡咯并吡咯的简便合成方法，该方法具有广泛的反应范围。合成了16种N-芳基二酮吡咯并吡咯，其中包括以苯基、呋喃和噻吩作为侧翼芳香基团的化合物，产率高达78%。这些N-芳基二酮吡咯并吡咯在溶液和固态中均具有荧光性，量子产率分别高达96%和40%。此外，我们还表明，以醋酸钯（Pd(OAc)）为催化剂，H-DPP与二芳基碘鎓盐之间的反应可生成π-扩展的二酮吡咯并吡咯。以27%-61%的产率获得了9种π-扩展的二酮吡咯并吡咯。这些π-扩展的二酮吡咯并吡咯表现出良好的半导体性能，空穴迁移率为0.71 cm² V⁻¹ s⁻¹，表明它们是用于高性能有机半导体的有用结构单元。
