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

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

doi:10.1038/s41467-024-55556-5

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

Nat Commun. 2025 Jan 2;16(1):186. doi: 10.1038/s41467-024-55556-5.

Authors

Jinji Zhang^#¹, Xiaojing Fang^#¹, Weiwei Niu^#², Yiming Yu¹, Yanlin Hu¹, Jiawen Sun¹, Ying Xu¹, Zhihua Zhou³, Heyuan Liu⁴, Xiaonan Fan⁴, Baishu Zheng⁵, Qing Jiang⁶, Guangwu Li^{7

8}, Wangdong Zeng⁹

Affiliations

¹ School of Materials Science and Engineering, Hunan University of Science and Technology, Xiangtan, China.
² Center of Single-Molecule Sciences, Institute of Modern Optics, Tianjin Key Laboratory of Micro-Scale Optical Information Science and Technology, College of Electronic Information and Optical Engineering, Nankai University, Tianjin, China.
³ Key Laboratory of Theoretical Organic Chemistry and Function Molecule of Ministry of Education, Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, China.
⁴ School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao, Shandong, China.
⁵ Key Laboratory of Theoretical Organic Chemistry and Function Molecule of Ministry of Education, Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, China. zbaishu@163.com.
⁶ College of Chemistry and Bioengineering, Hunan University of Science and Engineering, Yongzhou, China. qjiang198@163.com.
⁷ Center of Single-Molecule Sciences, Institute of Modern Optics, Tianjin Key Laboratory of Micro-Scale Optical Information Science and Technology, College of Electronic Information and Optical Engineering, Nankai University, Tianjin, China. ligw@nankai.edu.cn.
⁸ Shenzhen Research Institute of Nankai University, Shenzhen, China. ligw@nankai.edu.cn.
⁹ School of Materials Science and Engineering, Hunan University of Science and Technology, Xiangtan, China. wangdong.zeng@hnust.edu.cn.

^# Contributed equally.

Abstract

[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 (t_1/2 = 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.

Abstract

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