Aromaticity is a vital concept that governs the electronic properties of π-conjugated organic molecules and has long been restricted to 2D systems. The aromaticity in 3D π-conjugated molecules has been rarely studied. Here we report a fully conjugated diradicaloid molecular cage and its global aromaticity at different oxidation states. The neutral compound has an open-shell singlet ground state with a dominant 38π monocyclic conjugation pathway and follows the [4n + 2] Hückel aromaticity rule; the dication has a triplet ground state with a dominant 36π monocyclic conjugation pathway and satisfies [4n] Baird aromaticity; the tetracation is an open-shell singlet with 52 π-electrons that are delocalized along the 3D rigid framework, showing 3D global antiaromaticity; and the hexacation possesses D₃ symmetry with 50 globally delocalized π-electrons, showing [6n + 2] 3D global aromaticity. Different types of aromaticity were therefore accessed in one molecular cage platform, depending on the symmetry, number of π-electrons and spin state.

芳香性是控制 π 共轭有机分子电子特性的重要概念，长期以来一直局限于二维系统。很少研究 3D π 共轭分子中的芳香性。在这里，我们报告了一个完全共轭的双自由基分子笼及其在不同氧化态下的整体芳香性。中性化合物具有开壳单线态基态，具有主要的 38π 单环共轭途径，并遵循 [4 n  + 2] Hückel 芳香性规则；该双阳离子具有三重基态，具有占主导地位的 36π 单环共轭途径，并满足 [4 n] 贝尔德芳香；四阳离子是具有 52 个 π 电子的开壳单线态，沿 3D 刚性框架离域，显示出 3D 全局反芳香性；并且六进制具有50个全局离域π电子的D _{3对称性，显示出[6} n  + 2] 3D全局芳香性。因此，根据对称性、π电子数和自旋态，在一个分子笼平台中可以访问不同类型的芳香性。