Stable Peri-hexacene: A Long-Waited Open-Shell Graphene Fragment-Reference-Cited by-同舟云学术

Stable Peri-hexacene: A Long-Waited Open-Shell Graphene Fragment

Published:2024-08-29 Issue: Volume: Page:
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Author:

Zeng Wangdong¹,Zhang JinJi¹,Fang Xiaojing¹,Niu Weiwei²,Yu Yiming¹,Hu Yanlin¹,Sun Jiawen¹,Xu Ying¹,Zhou Zhihua¹,Zheng Baishu¹,Jiang Qing³,Li Guangwu⁴

Affiliation:

1. Hunan University of Science and Technology

2. Nankai University

3. Hunan University of Science and Engineering

4. Department of Chemistry, National University of Singapore

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 was unequivocally confirmed by X-ray crystallographic analysis. Its ground state, aromaticity and photophysical properties were 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 exhibited 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.

Publisher

Springer Science and Business Media LLC

Reference28 articles.

1. (a) Nakada K, Fujita M, Dresselhaus G, Dresselhaus MS Edge state in graphene ribbons: Nanometer size effect and edge shape dependence. Phys. Rev. B. 54, 17954–17961. (b) Son, Y. W.; Cohen, M. L.; Louie, S. G. Half-metallic graphene nanoribbons. Nature 2006, 444, 347–349. (c) Kumar, S.; Pratap, S.; Kumar, V.; Mishra, R. K.; Gwag, J. S.; Chakraborty, B. Electronic, transport, magnetic, and optical properties of graphene nanoribbons and their optical sensing applications: A comprehensive review. Luminescence 2023, 38, 909–953. (d) Mousavi, S. T.; Badehian, H. A.; Gharbavi, K. Optical spectra of zigzag graphene nanoribbons: a first-principles study. Phys. Scr. 2022, 97, NO. 105803. (e) Wang, Z.; Sun, M.; Zhao, Y.; Xiao, J.; Dai, X. The electronic and transport properties of the folded zigzag graphene nanoribbon. Surf. Interfaces. 2016, 5, 72–75. (f) Wang, X.-S.; Zhang, F.; Si, N.; Meng, J.; Zhang, Y.-L.; Jiang, W. Unique magnetic and thermodynamic properties of a zigzag graphene nanoribbon. Physica. A. 2019, 527, NO. 121356. (g) Son, Y. W.; Cohen, M. L.; Louie, S. G. Energy gaps in graphene nanoribbons. Phys. Rev. Lett. 2006, 97, NO. 216803. (h) Kan, E.-j.; Li Z, Yang J, Hou J, Paulus B, Tremblay (1996) Half-metallicity in edge-modified zigzag graphene nanoribbons. J. Am. Chem. Soc. 2008, 130, 4224–4225. (i) Zhang, D.-B.; Wei, S.-H. Inhomogeneous strain-induced half-metallicity in bent zigzag graphene nanoribbons. Npj. Comput. Mater. 2017, 3, 32–37. (j) Shao, J.; Paulus, B., Tremblay J. C. Local current analysis on defective zigzag graphene nanoribbons devices for biosensor material applications. J. Comput. Chem. 2021, 42, 1475–1485

2. Martín-Martínez FJ, Fias S, Hajgató B, Van Lier G, De Proft F, Geerlings P Inducing Aromaticity Patterns and Tuning the Electronic Transport of Zigzag Graphene Nanoribbons via Edge Design (eds) (2013) J. Phys. Chem. C. 117, 26371-26384. (b) Feng, J.

3. Bi, S. How size, edge shape, functional groups and embeddedness influence the electronic structure and partial optical properties of graphene nanoribbons. Phys. Chem. Chem. Phys. 2021, 23, 20695-20701. (c) Li, Z.

4. Duan, W. The half-metallicity of zigzag graphene nanoribbons with asymmetric edge terminations. J. Nanosci. Nanotechno. 2010, 10, 5374-5378

5. Martín-Martínez FJ, Fias S, Hajgató B, Van Lier G, De Proft F, Geerlings P Inducing Aromaticity Patterns and Tuning the Electronic Transport of Zigzag Graphene Nanoribbons via Edge Design (eds) (2013) J. Phys. Chem. C. 117, 26371-26384.