Yao Mengyu, Jing Yaru, Bi Hongyan, Ke Zhuofeng, Wang Sunewang R
Chang-Kung Chuang Institute, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200241, China.
School of Materials Science and Engineering, PCFM Lab, Key Laboratory of Low-carbon Chemistry & Energy Conservation of Guangdong Province, Sun Yat-sen University, Guangzhou 510006, China.
J Org Chem. 2024 Sep 20;89(18):13093-13100. doi: 10.1021/acs.joc.4c01180. Epub 2024 Sep 9.
Scorpion-shaped hybrid double helicenes, consisting of a [5] or [6] carbohelicene and an aza[4]helicene, have been successfully constructed by orthogonal alkyne annulations via an aryl C-I bond and amido N-H bond from polyaromatic ring-fused iodoisocoumarins. In spite of the unexpected instability upon aerobic oxidation upon ambient visible light irradiation over several days, both ultraviolet-visible absorption and photoluminescence spectra along with density functional theory calculations of these helicenes have been studied, which rely heavily on the bent polyaromatic ring-fused quinolizinone conjugate skeleton. In addition, the Stokes shifts of hybrid double helicenes are generally larger than those of the structurally similar mono-carbohelicenes.
由一个[5]或[6]碳并苯和一个氮杂[4]并苯组成的蝎形杂化双并苯，已通过芳基C-I键和酰胺基N-H键的正交炔烃环化反应，从多芳环稠合的碘代异香豆素成功构建。尽管在环境可见光照射下经过几天的有氧氧化会出现意外的不稳定性，但还是对这些并苯的紫外可见吸收光谱、光致发光光谱以及密度泛函理论计算进行了研究，这些研究很大程度上依赖于弯曲的多芳环稠合喹嗪酮共轭骨架。此外，杂化双并苯的斯托克斯位移通常比结构相似的单碳并苯的斯托克斯位移大。
