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<p>[n]<i>Peri</i>-acenes ([n]PA) have attracted great interest as promising candidates for nanoelectronics and spintronics. However, the synthesis of large [n]PA (<i>n</i> &gt; 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 <i>peri</i>-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 <i>peri</i>-hexacene is calculated to have a very large diradical character (<i>y</i><sub>0</sub> = 94.5%), 1 shows reasonable stability (<i>t</i><sub>1/2</sub> = 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.</p>

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

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年1月2日

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  • 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

摘要

[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.