Citation: Zhengzhong Zhu, Shaojun Hu, Zhi Liu, Lipeng Zhou, Chongbin Tian, Qingfu Sun. A cationic radical lanthanide organic tetrahedron with remarkable coordination enhanced radical stability[J]. Chinese Chemical Letters, ;2025, 36(2): 109641. doi: 10.1016/j.cclet.2024.109641 shu

A cationic radical lanthanide organic tetrahedron with remarkable coordination enhanced radical stability

Zhengzhong Zhu ^{a, b} ,
Shaojun Hu ^{a, b} ,
Zhi Liu ^a ,
Lipeng Zhou ^{a, b} ,
Chongbin Tian ^{a, b, *,} ,
Qingfu Sun ^{a, b, *,}

a.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
b.
University of the Chinese Academy of Sciences, Beijing 100049, China

tianchongbin@fjirsm.ac.cn

qfsun@fjirsm.ac.cn

Received Date: 15 January 2024
Revised Date: 30 January 2024
Accepted Date: 7 February 2024
Available Online: 13 February 2024

Figures(6)

Rare–earth supramolecular compounds, such as lanthanide organic polyhedrons (LOPs), are of particular interest due to their many possible applications in various fields. Here we report the first syntheses of Ln₄(L^•+)₄–type (Ln, lanthanides; L^•+, radical ligand) radical–bridged lanthanide organic tetrahedrons by self–assembly of face–capping triphenylamine (TPA)–cored radical ligand with different lanthanide ions. Remarkable coordination enhanced radical stability has been observed, with half–life times (t_1/2) for L₁^•+, La₄(L₁^•+)₄, Eu₄(L₁^•+)₄, Gd₄(L₁^•+)₄, Tb₄(L₁^•+)₄ and Lu₄(L₁^•+)₄ estimated to be 53 min, 482 min, 624 min, 1248 min, 822 min and 347 min, respectively. The TPA radical in Ln₄(L₁^•+)₄ containing paramagnetic Ln ions (Ln = Eu^Ⅲ, Gd^Ⅲ and Tb^Ⅲ) is observed to be more stable than that in Ln₄(L₁^•+)₄ (Ln = La^Ⅲ and Lu^Ⅲ) constructed by diamagnetic Ln ions. This difference in radical stability is possibly due to the magnetic interactions between paramagnetic Ln^Ⅲ ions and L₁^•+ ligands, as confirmed by electron paramagnetic resonance (EPR) in La₄(L)₄ (L = L₁ and L₁^•+) and Tb₄(L)₄ (L = L₁ and L₁^•+), and magnetic susceptibility measurements in Tb₄(L)₄ (L = L₁ and L₁^•+). Our study reveals the coordination of radical ligands with lanthanide ions can improve the radical stability, which is crucial for their applications.
- Supramolecular chemistry,
- Self–assembly,
- Lanthanide organic polyhedrons,
- Radical,
- Enhanced stability
1. [1]
  Y. Sun, C. Chen, J. Liu, et al., Chem. Soc. Rev. 49 (2020) 3889–3919. doi: 10.1039/D0CS00038H
2. [2]
  E.G. Percastegui, T.K. Ronson, J.R. Nitschke, Chem. Rev. 120 (2020) 13480–13544. doi: 10.1021/acs.chemrev.0c00672
3. [3]
  C.M. Hong, R.G. Bergman, K.N. Raymond, et al., Acc. Chem. Res. 51 (2018) 2447–2455. doi: 10.1021/acs.accounts.8b00328
4. [4]
  M.D. Ward, C.A. Hunter, N.H. Williams, Acc. Chem. Res. 51 (2018) 2073–2082. doi: 10.1021/acs.accounts.8b00261
5. [5]
  D.L. Caulder, K.N. Raymond, Acc. Chem. Res. 32 (1999) 975–982. doi: 10.1021/ar970224v
6. [6]
  M. Fujita, M. Tominaga, A. Hori, et al., Acc. Chem. Res. 38 (2005) 369–378. doi: 10.1021/ar040153h
7. [7]
  S. Bai, Y.F. Han, Acc. Chem. Res. 56 (2023) 1213–1227. doi: 10.1021/acs.accounts.3c00102
8. [8]
  C.T. McTernan, J.A. Davies, J.R. Nitschke, Chem. Rev. 122 (2022) 10393–10437. doi: 10.1021/acs.chemrev.1c00763
9. [9]
  C.B. Tian, Q.F. Sun, Chem. Eur. J. 29 (2023) e202300195. doi: 10.1002/chem.202300195
10. [10]
  Y. Domoto, M. Fujita, Coord. Chem. Rev. 466 (2022) 214605–214617. doi: 10.1016/j.ccr.2022.214605
11. [11]
  F. Wang, S. Bai, Q.W. Zhu, et al., CCS Chem. 5 (2023) 633–640. doi: 10.31635/ccschem.022.202201919
12. [12]
  K. Acharyya, S. Bhattacharyya, H. Sepehrpour, et al., J. Am. Chem. Soc. 141 (2019) 14565–14569. doi: 10.1021/jacs.9b08403
13. [13]
  P. Howlader, E. Zangrando, P.S. Mukherjee, J. Am. Chem. Soc. 142 (2020) 9070–9078. doi: 10.1021/jacs.0c03551
14. [14]
  M. Pan, K. Wu, J.H. Zhang, et al., Coord. Chem. Rev. 378 (2019) 333–349. doi: 10.1016/j.ccr.2017.10.031
15. [15]
  K. Wu, K. Li, S. Chen, et al., Angew. Chem. Int. Ed. 59 (2019) 2639–2643.
16. [16]
  J. Zhu, X. Chen, X. Jin, et al., Chin. Chem. Lett. 34 (2023) 108002–108005. doi: 10.1016/j.cclet.2022.108002
17. [17]
  Y.L. Lai, H.J. Zhang, J. Su, et al., Chin. Chem. Lett. 34 (2023) 107686–107690. doi: 10.1016/j.cclet.2022.07.029
18. [18]
  C. Li, Y. Wang, Y. Lu, et al., Chin. Chem. Lett. 31 (2020) 1183–1187. doi: 10.1016/j.cclet.2019.09.034
19. [19]
  D. Luo, B. Pan, J. Zhang, et al., Chin. Chem. Lett. 32 (2021) 1397–1399. doi: 10.1016/j.cclet.2020.11.002
20. [20]
  R.Y. Chen, Y.P. He, J. Zhang, Polyoxometalates 1 (2022) 9140002–9140007. doi: 10.26599/POM.2022.9140002
21. [21]
  R.Y. Chen, G.H. Chen, Y.P. He, et al., Chin. J. Struct. Chem. 41 (2022) 2201001–2201006.
22. [22]
  X. Liu, X. Feng, K.R. Meihaus, et al., Angew. Chem. Int. Ed. 59 (2020) 10610–10618. doi: 10.1002/anie.202002673
23. [23]
  D.J. Bell, L.S. Natrajan, I.A. Riddell, Coord. Chem. Rev. 472 (2022) 214786–214810. doi: 10.1016/j.ccr.2022.214786
24. [24]
  X.Z. Li, C.B. Tian, Q.F. Sun, Chem. Rev. 122 (2022) 6374–6458. doi: 10.1021/acs.chemrev.1c00602
25. [25]
  M.H. Du, D.H. Wang, L.W. Wu, et al., Angew. Chem. Int. Ed. 61 (2022) e202200537. doi: 10.1002/anie.202200537
26. [26]
  X.L. Li, J. Wu, L. Zhao, et al., Chem. Commun. 53 (2017) 3026–3029. doi: 10.1039/C7CC00048K
27. [27]
  X.L. Li, J. Wu, J. Tang, et al., Chem. Commun. 52 (2016) 9570–9573. doi: 10.1039/C6CC05326B
28. [28]
  J. Wang, C. He, P. Wu, et al., J. Am. Chem. Soc. 133 (2011) 12402–12405. doi: 10.1021/ja2048489
29. [29]
  D.E. Barry, D.F. Caffrey, T. Gunnlaugsson, Chem. Soc. Rev. 45 (2016) 3244–3274. doi: 10.1039/C6CS00116E
30. [30]
  J. Hamacek, A. Vuillamy, Eur. J. Inorg. Chem. 2018 (2017) 1155–1166.
31. [31]
  H.Y. Wong, W.S. Lo, K.H. Yim, et al., Chem 5 (2019) 3058–3095. doi: 10.1016/j.chempr.2019.08.006
32. [32]
  S.J. Hu, X.Q. Guo, L.P. Zhou, et al., J. Am. Chem. Soc. 144 (2022) 4244–4253. doi: 10.1021/jacs.2c00760
33. [33]
  S.J. Hu, X.Q. Guo, L.P. Zhou, et al., Chin. J. Chem. 41 (2023) 797–804. doi: 10.1002/cjoc.202200649
34. [34]
  B.S. Dolinar, D.I. Alexandropoulos, K.R. Vignesh, et al., J. Am. Chem. Soc. 140 (2018) 908–911. doi: 10.1021/jacs.7b12495
35. [35]
  D.I. Alexandropoulos, B.S. Dolinar, K.R. Vignesh, et al., J. Am. Chem. Soc. 139 (2017) 11040–11043. doi: 10.1021/jacs.7b06925
36. [36]
  X. Liu, Y. Zhang, W. Shi, et al., Inorg. Chem. 57 (2018) 13409–13414. doi: 10.1021/acs.inorgchem.8b01981
37. [37]
  X. Meng, W. Shi, P. Cheng, Coord. Chem. Rev. 378 (2019) 134–150. doi: 10.1016/j.ccr.2018.02.002
38. [38]
  E.T. Seo, R.F. Nelson, J.M. Fritsch, et al., J. Am. Chem. Soc. 88 (1966) 3498–3503. doi: 10.1021/ja00967a006
39. [39]
  D.H. Reid, Tetrahedron 3 (1958) 339–352. doi: 10.1016/0040-4020(58)80039-3
40. [40]
  S. Kumar, M.R. Ajayakumar, G. Hundal, et al., J. Am. Chem. Soc. 136 (2014) 12004–12010. doi: 10.1021/ja504903j
41. [41]
  P.P. Power, Chem. Rev. 103 (2003) 789–810. doi: 10.1021/cr020406p
42. [42]
  H. Garcia, H.D. Roth, Chem. Rev. 102 (2002) 3947–4007. doi: 10.1021/cr980026x
43. [43]
  V. Pushkara Rao, M.B. Zimmt, N.J. Turro, J. Photochem. Photobio. A: Chem. 60 (1991) 355–360. doi: 10.1016/1010-6030(91)90037-T
44. [44]
  H. Hu, Y.Y. Zhang, H. Ma, et al., Angew. Chem. Int. Ed. 62 (2023) e202308513. doi: 10.1002/anie.202308513
45. [45]
  E. Breinlinger, A. Niemz, V.M. Rotello, J. Am. Chem. Soc. 117 (1995) 5379–5380. doi: 10.1021/ja00124a029
46. [46]
  Q. Song, F. Li, Z. Wang, et al., Chem. Sci. 6 (2015) 3342–3346. doi: 10.1039/C5SC00862J
47. [47]
  E. Moulin, F. Niess, M. Maaloum, et al., Angew. Chem. Int. Ed. 49 (2010) 6974–6978. doi: 10.1002/anie.201001833
48. [48]
  Z. Feng, S. Tang, Y. Su, et al., Chem. Soc. Rev. 51 (2022) 5930–5973. doi: 10.1039/D2CS00288D
49. [49]
  G. Huo, X. Shi, Q. Tu, et al., J. Am. Chem. Soc. 141 (2019) 16014–16023. doi: 10.1021/jacs.9b08149
50. [50]
  Q. Tu, G.F. Huo, X.L. Zhao, et al., Mat. Chem. Front. 5 (2021) 1863–1871. doi: 10.1039/D0QM00992J
51. [51]
  S.K. Zhang, L.Z. Ma, W.Q. Ma, et al., Angew. Chem. Int. Ed. 61 (2022) e202209054. doi: 10.1002/anie.202209054
52. [52]
  K. Yazaki, S. Noda, Y. Tanaka, et al., Angew. Chem. Int. Ed. 55 (2016) 15031–15034. doi: 10.1002/anie.201608350
53. [53]
  Z. Lu, R. Lavendomme, O. Burghaus, et al., Angew. Chem. Int. Ed. 58 (2019) 9073–9077. doi: 10.1002/anie.201903286
54. [54]
  G.F. Jin, Y.Z. Zhang, L. Yu, et al., Nano Res. 16 (2023) 10678–10683. doi: 10.1007/s12274-023-5690-2
55. [55]
  J. Wang, K. Liu, L. Ma, et al., Chem. Rev. 116 (2016) 14675–14725. doi: 10.1021/acs.chemrev.6b00432
56. [56]
  G. Tan, X. Wang, Acc. Chem. Res. 50 (2017) 1997–2006. doi: 10.1021/acs.accounts.7b00229
57. [57]
  E. Moulin, J.J.T. Armao, N. Giuseppone, Acc. Chem. Res. 52 (2019) 975–983. doi: 10.1021/acs.accounts.8b00536
58. [58]
  L. Mao, M. Zhou, X. Shi, et al., Chin. Chem. Lett. 32 (2021) 3331–3341. doi: 10.1016/j.cclet.2021.05.004
59. [59]
  B. Huang, L. Mao, X. Shi, et al., Chem. Sci. 12 (2021) 13648–13663. doi: 10.1039/D1SC01618K
60. [60]
  W.L. Jiang, Z. Peng, B. Huang, et al., J. Am. Chem. Soc. 143 (2021) 433–441. doi: 10.1021/jacs.0c11738
61. [61]
  Z.X. Chen, Y. Li, F. Huang, Chem 7 (2021) 288–332. doi: 10.1016/j.chempr.2020.09.024
62. [62]
  Ł. Skórka, J.M. Mouesca, J.B. Gosk, et al., J. Mater. Chem. C 5 (2017) 6563–6569. doi: 10.1039/C7TC01932G
63. [63]
  M. Uebe, T. Kazama, R. Kurata, et al., Angew. Chem. Int. Ed. 56 (2017) 15712–15717. doi: 10.1002/anie.201709874
64. [64]
  Y. Yokoyama, D. Sakamaki, A. Ito, et al., Angew. Chem. Int. Ed. 51 (2012) 9403–9406. doi: 10.1002/anie.201204106
65. [65]
  X. Li, Y.L. Wang, C. Chen, et al., Chemistry 29 (2023) e202203242. doi: 10.1002/chem.202203242
66. [66]
  X. Li, Y.L. Wang, C. Chen, et al., Nat. Commun. 13 (2022) 5367–5374. doi: 10.1038/s41467-022-33130-1
67. [67]
  X.Q. Guo, L.P. Zhou, L.X. Cai, et al., Chem. Eur. J. 24 (2018) 6936–6940. doi: 10.1002/chem.201801132
68. [68]
  L.L. Yan, C.H. Tan, L.P. Zhou, et al., J. Am. Chem. Soc. 137 (2015) 8550–8555. doi: 10.1021/jacs.5b03972
69. [69]
  T. Lu, F. Chen, J. Comput. Chem. 33 (2012) 580–592. doi: 10.1002/jcc.22885
70. [70]
  W.Y. Sun, T. Kusukawa, M. Fujita, J. Am. Chem. Soc. 124 (2002) 11570–11571. doi: 10.1021/ja0206285
71. [71]
  K. Sreenath, C.V. Suneesh, V.K. Kumar, et al., J. Org. Chem. 73 (2008) 3245–3251. doi: 10.1021/jo800349n
72. [72]
  S. Zheng, S. Barlow, C. Risko, et al., J. Am. Chem. Soc. 128 (2006) 1812–1817. doi: 10.1021/ja0541534
73. [73]
  Y. Satoh, L. Catti, M. Akita, et al., J. Am. Chem. Soc. 141 (2019) 12268–12273. doi: 10.1021/jacs.9b03419
74. [74]
  V. Croue, S. Goeb, G. Szaloki, et al., Angew. Chem. Int. Ed. 55 (2016) 1746–1750. doi: 10.1002/anie.201509265
75. [75]
  J.E. McPeak, S.S. Eaton, G.R. Eaton, Methods Enzymol. 651 (2021) 63–101.
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