Jishan Wu

The exploration of annulene's conformation, electronic properties and aromaticity has generated enduring interest over the years, yet it continues to present formidable challenges for annulenes with more than ten carbon atoms. In this study, we present the synthesis of a stable [10]cyclo‐ para ‐phenylmethine derivative ( 1 ), which bears a resemblance to [10]annulene. 1 can be readily oxidized into its respective cations, wherein electrons are effectively delocalized along the backbone, resulting in different conformations and aromaticity. Both 1 and its tetracation ( 1 4+ ⋅ 4SbF 6 − ) exhibit a nearly planar conformation with a rectangular shape, akin to the E , Z , E ,Z, Z ‐[10]annulene. In contrast, the radical cation ( 1 ⋅ + ⋅ SbCl 6 − ) possesses a doubly twisted Hückel topology. Furthermore, the dication ( 1 2+ ⋅ 2SbCl 6 − ) displays conformational flexibility in solution and crystalizes with the simultaneous presence of Möbius‐twisted ( 1a 2+ ⋅ 2SbCl 6 − ) and Hückel‐planar ( 1b 2+ ⋅ 2SbCl 6 − ) isomers in its unit cell. Detailed experimental measurements and theoretical calculations reveal that: (1) 1 demonstrates localized aromaticity with an alternating benzenoid/quinoid structure; (2) 1a 2+ ⋅ 2SbCl 6 − and 1b 2+ ⋅ 2SbCl 6 − with 48π electrons are weakly Möbius aromatic and Hückel antiaromatic, respectively; (3) 1 4+ ⋅ 4SbF 6 − exhibits Hückel aromaticity (46π) and open‐shell diradical character.