Citation: Chenwei Li, Yijian Ma, Jun Yu, Jing Liu, Jiang Wang, Jiajia Liu, Kailiang Ding, Manman Sun, Chengshuo Shen, Xunshan Liu, Maozhong Miao. Two-fold gold(I)-catalyzed 7-endo-dig annulation toward synthesis of curved azepine-embedded nanographenes[J]. Chinese Chemical Letters, ;2026, 37(6): 111719. doi: 10.1016/j.cclet.2025.111719 shu

Two-fold gold(I)-catalyzed 7-endo-dig annulation toward synthesis of curved azepine-embedded nanographenes

Chenwei Li ^{a, 1} ,
Yijian Ma ^{a, 1} ,
Jun Yu ^{a, 1} ,
Jing Liu ^a ,
Jiang Wang ^a ,
Jiajia Liu ^a ,
Kailiang Ding ^a ,
Manman Sun ^b ,
Chengshuo Shen ^{a, *,} ,
Xunshan Liu ^{a, *,} ,
Maozhong Miao ^{a, *,}

a.
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China
b.
Advanced Research Institute and School of Pharmaceutical Science, Taizhou University, Jiaojiang 318000, China

shenchengshuo@zstu.edu.cn

xliu350@zstu.edu.cn

mmzok@zstu.edu.cn

Received Date: 16 May 2025
Revised Date: 26 July 2025
Accepted Date: 12 August 2025
Available Online: 13 August 2025

Figures(5)

Nanographenes (NGs) incorporating N-doped heptagonal units demonstrate intriguing physicochemical properties, attributed to their negatively curved structure induced by the angular strain of the heptagons and the electronic effects of nitrogen atoms, while their precise synthesis remains a challenging task. Herein, we developed an efficient approach for the construction of azepine-embedded NGs via two-fold S_NAr/gold(I)-catalyzed 7-endo-dig annulation from commercially available 4,7-dibromo-5,6-difluorobenzo[2,1,3]thiadiazole. The fusion of two heptagonal rings dramatically increases the intramolecular strain and forces the central skeleton to twist, giving rise to a unique packing mode in the crystal. The incorporation of thiadiazole leads to a pronounced bathochromic shift in the fluorescence emission, which causes the typical product to display NIR-emission. Furthermore, it is found that the backbone core of these NGs with thiadiazole exhibits excellent single-molecule conductivity as well.
- Gold catalysis,
- 7-endo-dig annulation,
- Azepine-embedded NGs,
- Negative curvature,
- NIR-emission
1. [1]
  Z.S. Wu, Y.Z. Tan, S. Zheng, et al., J. Am. Chem. Soc. 139 (2017) 4506-4512. doi: 10.1021/jacs.7b00805
2. [2]
  M. Takeda, S. Hiroto, H. Yokoi, et al., J. Am. Chem. Soc. 140 (2018) 6336-6342. doi: 10.1021/jacs.8b02327
3. [3]
  H.A. Lin, Y. Sato, Y. Segawa, et al., Angew. Chem. Int. Ed. 57 (2018) 2874-2878. doi: 10.1002/anie.201713387
4. [4]
  Y. Wang, Z.G. Wu, F. Shi, Chem. Cat. 2 (2022) 3077-3111.
5. [5]
  H. Shi, B. Xiong, Y. Chen, et al., Chin. Chem. Lett. 34 (2023) 107520. doi: 10.1016/j.cclet.2022.05.034
6. [6]
  W. Cui, Z. Jin, W. Fu, C. Shen, Chin. Chem. Lett. 35 (2024) 109667. doi: 10.1016/j.cclet.2024.109667
7. [7]
  E.M. Muzammil, D. Halilovic, M.C. Stuparu, Commun. Chem. 2 (2019) 58. doi: 10.1038/s42004-019-0160-1
8. [8]
  S.H. Pun, Q. Miao, Acc. Chem. Res. 51 (2018) 1630-1642. doi: 10.1021/acs.accounts.8b00140
9. [9]
  I.R. Márquez, S. Castro-Fernández, A. Millán, et al., Chem. Commun. 54 (2018) 6705-6718. doi: 10.1039/c8cc02325e
10. [10]
  Chaolumen, I.A. Stepek, K.E. Yamada, et al., Angew. Chem. Int. Ed. 60 (2021) 23508-23532. doi: 10.1002/anie.202100260
11. [11]
  G. González Miera, S. Matsubara, H. Kono, et al., Chem. Sci. 13(2022) 1848-1868. doi: 10.1039/d1sc05586k
12. [12]
  S.H. Pun, Y. Wang, M. Chu, et al., J. Am. Chem. Soc. 141 (2019) 9680-9686. doi: 10.1021/jacs.9b03910
13. [13]
  K.Y. Cheung, Q. Miao, Chin. Chem. Lett. 30 (2019) 1506-1508. doi: 10.1016/j.cclet.2019.04.013
14. [14]
  B. Liu, M. Chen, X. Liu, et al., J. Am. Chem. Soc. 145 (2023) 28137-28145. doi: 10.1021/jacs.3c10303
15. [15]
  M. Rickhaus, M. Mayor, M. Jurícek, Soc. Rev. 46 (2017) 1643-1660. doi: 10.1039/C6CS00623J
16. [16]
  K. Kato, K. Takaba, S. Maki-Yonekura, et al., J. Am. Chem. Soc. 143 (2021) 5465-5469. doi: 10.1021/jacs.1c00863
17. [17]
  J. Liu, S. Mishra, C.A. Pignedoli, et al., J. Am. Chem. Soc. 141 (2019) 12011-12020. doi: 10.1021/jacs.9b04718
18. [18]
  M.W. Wang, Z. Li, Y. Liu, et al., Org. Chem. Front. 10 (2023) 2808-2812. doi: 10.1039/d3qo00202k
19. [19]
  J. Liu, X. Feng, Synlett. 31 (2020) 211–222. doi: 10.1055/s-0039-1690767
20. [20]
  A. Borissov, Y.K. Maurya, L. Moshniaha, et al., Chem. Rev. 122 (2022) 565–788. doi: 10.1021/acs.chemrev.1c00449
21. [21]
  K. Bartkowski, P.Z. Crocomo, M.A. Kochman, et al., Chem. Sci. 13 (2022) 10119–10128. doi: 10.1039/d2sc03342a
22. [22]
  X. Tian, K. Shoyama, F. Würthner, Chem. Sci. 14 (2023) 284–290. doi: 10.1039/d2sc05409d
23. [23]
  L. Ruan, W. Luo, H. Zhang, et al., Chem. Sci. 15 (2024) 1511. doi: 10.1039/d3sc05515a
24. [24]
  M. Krezeszewski, Ł. Dobrzycki, A.L. Sobolewski, et al., Angew. Chem. Int. Ed. 60 (2021) 1499815005.
25. [25]
  J. Wagner, P.Z. Crocomo, M.A. Kochman, et al., Angew. Chem. Int. Ed. 61 (2022) e202202232. doi: 10.1002/anie.202202232
26. [26]
  D. Hellwinkel, H. Seifert, Chem. Ber. 105(1972) 880-906. doi: 10.1002/cber.19721050320
27. [27]
  C. Wang, Z. Deng, D.L. Phillips, J. Liu, Angew. Chem. Int. Ed. 62 (2023) e202306890. doi: 10.1002/anie.202306890
28. [28]
  S. Qiu, A.C. Valdivia, W. Zhuang, et al., J. Am. Chem. Soc. 146 (2024) 16161-16172. doi: 10.1021/jacs.4c03815
29. [29]
  F. Gan, G. Zhang, J. Liang, C. Shen, H. Qiu, Angew. Chem. Int. Ed. 63 (2024) e202320076. doi: 10.1002/anie.202320076
30. [30]
  H. Luo, J. Liu, Angew. Chem. Int. Ed. 63 (2024) e202410759.
31. [31]
  C.M. Hendrich, K. Sekine, T. Koshikawa, et al., Chem. Rev. 121 (2021) 9113-9163. doi: 10.1021/acs.chemrev.0c00824
32. [32]
  S. Zhang, A. Tang, P. Chen, et al., Org. Lett. 22 (2020) 848-853. doi: 10.1021/acs.orglett.9b04312
33. [33]
  S. Zhang, R. Xie, A. Tang, et al., Org. Lett. 22 (2020) 3056-3061. doi: 10.1021/acs.orglett.0c00810
34. [34]
  J. Zhang, T. Lu, Chem. Chem. Phys. 23 (2021) 20323-20328. doi: 10.1039/d1cp02805g
35. [35]
  T. Lu, Q. Chen, J. Comput. Chem. 43 (2022) 539-555. doi: 10.1002/jcc.26812
36. [36]
  M.J. Frisch, G.W. Trucks, H.B. Schlegel, et al., Gaussian 09, 2013 Revision E.01, Wallingford CT.
37. [37]
  T. Lu, F. Chen, Chem. J. Comput. Chem. 33 (2012) 580-592. doi: 10.1002/jcc.22885
38. [38]
  T. Lu, J. Chem. Phys. 161 (2024) 082503.
39. [39]
  Z. Liu, T. Lu, Q. Chen, Carbon 165 (2020) 461-467. doi: 10.1016/j.carbon.2020.05.023
40. [40]
  S. Li, C. Yin, R. Wang, et al., ACS Appl. Mater. Interfaces 12 (2020) 20281-20286. doi: 10.1021/acsami.0c03769
41. [41]
  J. Cui, F. Zhang, D. Yan, et al., Adv. Mater. 35 (2023) 2302639. doi: 10.1002/adma.202302639
42. [42]
  M. Liang, L. Liu, Y. Sun, et al., Aggregate 5 (2024) e458. doi: 10.1002/agt2.458
43. [43]
  B. Li, W. Wang, L. Zhao, et al., Adv. Mater. 36 (2024) 2305378. doi: 10.1002/adma.202305378
44. [44]
  W. Chen, H. Li, J.R. Widawsky, et al., J. Am. Chem. Soc. 136 (2014) 918-920. doi: 10.1021/ja411143s
45. [45]
  L. Chen, Z. Yang, Q. Lin, et al., Langmuir 40 (2024) 1988-2004. doi: 10.1021/acs.langmuir.3c03104
46. [46]
  B. Wang, C. Chen, Y. Huo, et al., J. Am. Chem. Soc. 147 (2025) 7809-7816. doi: 10.1021/jacs.4c17477
47. [47]
  A. Feng, Y. Zhou, M.A. Y. Al-Shebami, et al., Nat. Chem. 14 (2022) 1158-1164. doi: 10.1038/s41557-022-01003-1
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