We present the oxidative transformation of a corrole isomer, namely, dibenzocorrorin (3), featuring a modified connectivity pattern of bipyrrole moieties within the corrole scaffold, resulting in the formation of pyrrole-embedded polycyclic molecules (1 and 2). The X-ray crystallography analysis of compound 1 revealed the establishment of three C–N bonds through nitrogen sites in the pyrrole and indole rings, leading to a highly π-conjugated core with nine fused aromatic rings. Notably, the β-pyrrole protons of the diazadicyclopentaazulene moiety displayed significant high-field shifts in the ¹H-NMR spectrum, attributed to the 12π antiaromatic contribution of the diazadicyclopentaazulene segment, as indicated by NICS and ACID plot analyses. Compound 1 exhibited a broad near-infrared absorption beyond 1000 nm, a narrow electrochemical energy gap (ΔE = 1.15 V), a short excited-state lifetime, and stable photothermal conversion capability. The crystalline packing structure of 1, characterized by staircase-like stacking along the long axis of needle-shaped crystals, facilitated the fabrication of a single-crystal organic field-effect transistor. The resulting device demonstrated p-type semiconductor behaviour, emphasizing the potential of 1 in near-infrared optoelectronic applications.

中文翻译：

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通过铜介导的裂解和环化将苯并甲苯醚异构体转化为含吡咯的多环分子


我们介绍了 corrole 异构体，即二苯并 corrorin （3） 的氧化转化，其特征是 corrole 支架内双吡咯部分的修饰连接模式，导致形成吡咯包埋的多环分子 （1 和 2）。化合物 1 的 X 射线晶体学分析揭示了通过吡咯环和吲哚环中的氮位点建立三个 C-N 键，导致具有 9 个熔融芳香环的高度π共轭核心。值得注意的是，二氮杂二环五氮杂烯部分的 β-吡咯质子在 ¹H-NMR 谱中显示出显着的高场偏移，这归因于二氮杂二环五氮杂烯链段的 12π 反芳烃贡献，如 NICS 和 ACID 图分析所示。化合物 1 表现出超过 1000 nm 的宽近红外吸收、较窄的电化学能隙 （ΔE = 1.15 V）、短激发态寿命和稳定的光热转换能力。1 的晶体堆积结构，其特征是沿针状晶体的长轴呈阶梯状堆叠，有助于制造单晶有机场效应晶体管。所得器件展示了 p 型半导体行为，强调了 1 在近红外光电应用中的潜力。