A stable open-shell peri-hexacene with remarkable diradical character

作者：Jinji Zhang, Xiaojing Fang, Weiwei Niu, Yiming Yu, Yanlin Hu, Jiawen Sun, Ying Xu, Zhihua Zhou, Heyuan Liu, Xiaonan Fan, Baishu Zheng, Qing Jiang, Guangwu Li, Wangdong Zeng · 发表于：Nature Communications · 年份：2025 · DOI：10.1038/s41467-024-55556-5 · 被引用次数：10 · 研究领域：Synthesis and Properties of Aromatic Compounds、Graphene research and applications、Fullerene Chemistry and Applications

[n]Peri-acenes ([n]PA) have attracted great interest as promising candidates for nanoelectronics and spintronics. However, the synthesis of large [n]PA (n > 4) is extremely challenging due to their intrinsic open-shell radical character and high reactivity. Herein, we report the successful synthesis and isolation of a derivative (1) of peri-hexacene in crystalline form. The structure of 1 is unequivocally confirmed by X-ray crystallographic analysis. Its ground state, aromaticity and photophysical properties are systematically studied by both experimental methods and theoretical calculations. Although the parent peri-hexacene is calculated to have a very large diradical character (y0 = 94.5%), 1 shows reasonable stability (t1/2 = 24 h under ambient conditions) due to the kinetic blocking. 1 exhibits an open-shell singlet ground state with a small singlet-triplet energy gap (−1.33 kcal/mol from SQUID measurements). 1 has also a narrow HOMO-LUMO energy gap (1.05 eV) and displays amphoteric redox behavior. This work opens new avenues for the design and synthesis of stable zigzag-edged graphene-like molecules with significant diradical character. [n]Peri-acenes have attracted interest as promising candidates for nanoelectronics and spintronics but the synthesis of large (n > 4) [n]peri-acenes is extremely challenging due to their intrinsic open-shell radical character and high reactivity. Herein, the authors report the synthesis and isolation of a derivative of peri-hexacene in c...