Zhang Xi-Sha, Huang Yan-Ying, Zhang Jing, Meng Wei, Peng Qian, Kong Ruirui, Xiao Zhenwei, Liu Jie, Huang Miaofei, Yi Yuanping, Chen Liangliang, Fan Qingrui, Lin Gaobo, Liu Zitong, Zhang Guanxin, Jiang Lang, Zhang Deqing
Beijing National Laboratory for Molecular Sciences, Organic Solids Laboratory, 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. 2020 Feb 24;59(9):3529-3533. doi: 10.1002/anie.201914416. Epub 2020 Jan 22.
Polycyclic aromatic hydrocarbons with hexagons/pentagons or hexagons/heptagons have been intensively investigated in recent years, but those with simultaneous presence of hexagons, pentagons and heptagons remain rare. In this paper, we report dicyclohepta[ijkl,uvwx]rubicene (DHR), a non-benzenoid isomer of dibenzo[bc,kl]coronene with two pentagons and two heptagons. We developed an efficient and scalable synthetic method for DHR by using Scholl reaction and dehydrogenation. Crystal structure of DHR shows that the benzenoid rings, two pentagons and two heptagons are coplanar. The bond lengths analysis and the ICSS(1)zz and LOL-π calculations indicate that the incorporation of two formal azulene moieties has an effect on the conjugated structure. The π-electrons of benzenoid and pentagon rings are more delocalized. Cyclic voltammetry studies indicate that DHR shows multiple oxidation and reduction potentials. Interestingly, DHR exhibits unusual S to S absorption and abnormal anti-Kasha S to S emission. Moreover, crystals of DHR exhibit semiconducting behaviour with hole mobility up to 0.082 cm V s .
近年来，含有六边形/五边形或六边形/七边形的多环芳烃受到了广泛研究，但同时含有六边形、五边形和七边形的多环芳烃仍然很少见。在本文中，我们报道了二环庚[ijkl,uvwx]红荧烯（DHR），它是二苯并[bc,kl]蒄的一种非苯型异构体，含有两个五边形和两个七边形。我们通过使用肖尔反应和脱氢反应开发了一种高效且可扩展的DHR合成方法。DHR的晶体结构表明，苯环、两个五边形和两个七边形是共面的。键长分析以及ICSS(1)zz和LOL-π计算表明，两个形式上的薁部分的引入对共轭结构有影响。苯环和五边形环的π电子离域程度更高。循环伏安法研究表明，DHR显示出多个氧化和还原电位。有趣的是，DHR表现出不寻常的S到S吸收和异常的反卡莎S到S发射。此外，DHR晶体表现出半导体行为，空穴迁移率高达0.082 cm² V⁻¹ s⁻¹ 。
