π-Conjugated molecules with an annulene-within-an-annulene (AWA) super-ring structure have been pursued by chemists for a long time but with limited success. Here, we report the synthesis of two stable cyclopenta-ring-fused oligo(m-phenylene) macrocycles, 8MC-M and 10MC-M, both showing moderate polyradical character. The octaradicaloid 8MC-M exhibits a [24]annulene-within-[32]annulene structure, which is globally aromatic despite the fact that it possesses 4n π-electrons. Theoretical analyses reveal that the π-electrons in the inner and outer rings follow Baird's rule such that both are triplet biradicals, and overall the molecule is a ground-state spin singlet. The decaradicaloid 10MC-M also possesses a super-aromatic AWA structure with 30 and 40 π-electrons in the inner and outer rings, respectively. However, it has a triplet ground state with a singlet inner ring satisfying Hückel's rule and a triplet outer ring following Baird's rule. Therefore, molecules with a decoupled AWA super-ring structure are eventually attained and also show unusual global aromaticity.

化学家们长期以来一直在研究具有环-环-环内（AWA）超级环结构的π共轭分子，但获得的成功有限。这里，我们报告两个稳定环戊二烯环的稠合的寡核苷酸（合成米亚苯基）大环化合物，8MC-M和10MC-M ，二者示出了中等多基字符。八面体类化合物8MC-M表现出[24]环-[32]环中的环结构，尽管它具有4个nπ电子，但总体上是芳香族的。理论分析表明，内环和外环中的π电子均遵循贝尔德定律，因此两者均为三重态双自由基，整个分子均为基态自旋单重态。蜕皮类化合物10MC -M还具有内环和外环分别具有30和40个π电子的超芳族AWA结构。但是，它具有三重态基态，其单重态内环满足Hückel规则，三重态外环遵循Baird规则。因此，最终获得了具有解耦的AWA超级环结构的分子，并且还显示出异常的整体芳香性。