Citation: Qian-Cheng Luo, Xia-Li Ding, Wen-Jie Xu, Yuan-Qi Zhai, Yan-Zhen Zheng. Equatorial aminopyridine ligands stabilize an unusual straightly bridging mode in dimeric dysprosium(Ⅲ) single-molecule magnets[J]. Chinese Chemical Letters, ;2025, 36(9): 110304. doi: 10.1016/j.cclet.2024.110304 shu

Equatorial aminopyridine ligands stabilize an unusual straightly bridging mode in dimeric dysprosium(Ⅲ) single-molecule magnets

Qian-Cheng Luo ^{a, 1} ,
Xia-Li Ding ^{a, b, 1} ,
Wen-Jie Xu ^{a, 1} ,
Yuan-Qi Zhai ^a ,
Yan-Zhen Zheng ^{a, *,}

a.
Frontier Institute of Science and Technology, State Key Laboratory of Electrical Insulation and Power Equipment, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Xi’an Key Laboratory of Electronic Devices and Material Chemistry, and School of Chemistry, Xi’an Jiaotong University, Xi’an 710054, China
b.
Shaanxi Science and Technology Holding Institute, Xi’an 710016, China

zheng.yanzhen@xjtu.edu.cn

Received Date: 24 May 2024
Revised Date: 24 June 2024
Accepted Date: 30 July 2024
Available Online: 2 August 2024

Figures(7)

Due to the ionic feature of the lanthanide ions, to straightly bridge two lanthanide (Ln) ions is rather challenging though this bridging mode is much beneficial to suppress the zero-field quantum tunneling of the magnetization (QTM) for single-molecule magnets (SMMs), a kind of nanosized magnetic materials for high-density information storage and magnetic resonance imaging contrast agent. Here we used an unusual terminal amino pyridine ligand which utilizes extensive supramolecular interactions to stabilize such an unusual linear bridging mode and obtained a series of such dimeric Ln(Ⅲ) complexes - {[LnL_A(4-NH₂py)₅]₂(µ-Cl)}[BPh₄]₃ (For L_A^- = 1-AdO^-, 1Ln; for L_A^- = ^tBuO^-, 2Ln; Ln = Dy, Gd). More uniquely, the bridging chloride sits in the center of two improper rotation symmetry related Ln(Ⅲ) ions with local C_5v symmetry. The dimeric compounds 1Dy and 2Dy exhibit much slower low-temperature magnetic relaxation and thousands of times longer relaxation times at 2 K (τ_2K = 2706.89 and 1437.05 s for 1Dy and 2Dy) compared to the diluted ones with the approaching magnetic property of the C_5v motifs (τ_2K = 0.77 and 1.29 s for 1Dy@1Y and 2Dy@2Y). Though magnetic interactions mediated via the chloride bridge in both 1Dy and 2Dy are weak and antiferromagnetic, it is still very effective due to such a linear geometry to reduce the QTM effect in SMMs.
- Single-molecule magnets,
- Lanthanide complexes,
- Slow magnetic relaxation,
- Magnetic coupling,
- Quantum tunneling of the magnetization
1. [1]
  V. Vieru, S. Gómez-Coca, E. Ruiz, L.F. Chibotaru, Angew. Chem. Int. Ed. 63 (2024) e202303146. doi: 10.1002/anie.202303146
2. [2]
  T.G. Ashebr, H. Li, X. Ying, et al., ACS Mater. Lett. 4 (2022) 307–319. doi: 10.1021/acsmaterialslett.1c00765
3. [3]
  D. Parker, E.A. Suturina, I. Kuprov, N.F. Chilton, Acc. Chem. Res. 53 (2020) 1520–1534. doi: 10.1021/acs.accounts.0c00275
4. [4]
  A. Zabala-Lekuona, J.M. Seco, E. Colacio, Coord. Chem. Rev. 441 (2021) 213984. doi: 10.1016/j.ccr.2021.213984
5. [5]
  K.L.M. Harriman, D. Errulat, M. Murugesu, Trends Chem. 1 (2019) 425–439. doi: 10.1016/j.trechm.2019.04.005
6. [6]
  D.N. Woodruff, R.E.P. Winpenny, R.A. Layfield, Chem. Rev. 113 (2013) 5110–5148. doi: 10.1021/cr400018q
7. [7]
  F.S. Guo, B.M. Day, Y.C. Chen, et al., Science 362 (2018) 1400–1403. doi: 10.1126/science.aav0652
8. [8]
  C.A.P. Goodwin, F. Ortu, D. Reta, N.F. Chilton, D.P. Mills, Nature 548 (2017) 439–442. doi: 10.1038/nature23447
9. [9]
  Y.S. Ding, N.F. Chilton, R.E.P. Winpenny, Y.Z. Zheng, Angew. Chem. Int. Ed. 55 (2016) 16071–16074. doi: 10.1002/anie.201609685
10. [10]
  Y.D. Wang, Q.C. Luo, Y.Z. Zheng, Angew. Chem. Int. Ed. 63 (2024) e202407016. doi: 10.1002/anie.202407016
11. [11]
  Y.C. Chen, J.L. Liu, L. Ungur, et al., J. Am. Chem. Soc. 138 (2016) 2829–2837. doi: 10.1021/jacs.5b13584
12. [12]
  Z. Zhu, C. Zhao, T. Feng, et al., J. Am. Chem. Soc. 143 (2021) 10077–10082. doi: 10.1021/jacs.1c05279
13. [13]
  Z. Zhu, J. Tang, Natl. Sci. Rev. 9 (2022) nwac194. doi: 10.1093/nsr/nwac194
14. [14]
  Z. Zhu, J. Tang, Chem. Soc. Rev. 51 (2022) 9469–9481. doi: 10.1039/d2cs00516f
15. [15]
  Z. Hu, Y. Wang, A. Ullah, et al., Chem 9 (2023) 3613–3622. doi: 10.1016/j.chempr.2023.08.007
16. [16]
  C.A. Gould, K.R. Mcclain, D. Reta, et al., Science 375 (2022) 198–202. doi: 10.1126/science.abl5470
17. [17]
  P.B. Jin, Y.Q. Zhai, K.X. Yu, R.E.P. Winpenny, Y.Z. Zheng, Angew. Chem. Int. Ed. 59 (2020) 9350–9354. doi: 10.1002/anie.202001401
18. [18]
  Y.S. Ding, T. Han, Y.Q. Zhai, et al., Chem. Eur. J. 26 (2020) 5893–5902. doi: 10.1002/chem.202000646
19. [19]
  X.D. Huang, X.F. Ma, L.M. Zheng, Angew. Chem. Int. Ed. 62 (2023) e202300088. doi: 10.1002/anie.202300088
20. [20]
  A.B. Canaj, S. Dey, E.R. Martí, et al., Angew. Chem. Int. Ed. 58 (2019) 14146–14151. doi: 10.1002/anie.201907686
21. [21]
  X.L. Ding, Y.Q. Zhai, T. Han, et al., Chem. Eur. J. 27 (2021) 2623–2627. doi: 10.1002/chem.202003931
22. [22]
  J.L. Liu, Y.C. Chen, M.L. Tong, Chem. Soc. Rev. 47 (2018) 2431–2453. doi: 10.1039/c7cs00266a
23. [23]
  J.L. Liu, Y.C. Chen, Y.Z. Zheng, et al., Chem. Sci. 4 (2013) 3310–3316. doi: 10.1039/c3sc50843a
24. [24]
  Q.C. Luo, N. Ge, Y.Q. Zhai, et al., Chin. Chem. Lett. 34 (2023) 107547. doi: 10.1016/j.cclet.2022.05.061
25. [25]
  A.P. Orlova, M.S. Varley, M.G. Bernbeck, et al., J. Am. Chem. Soc. 145 (2023) 22265–22275. doi: 10.1021/jacs.3c08946
26. [26]
  W. Deng, S.N. Du, Z.Y. Ruan, et al., Aggregate 5 (2024) e441. doi: 10.1002/agt2.441
27. [27]
  K.X. Yu, J.G.C. Kragskow, Y.S. Ding, et al., Chem 6 (2020) 1777–1793. doi: 10.1016/j.chempr.2020.04.024
28. [28]
  X.L. Ding, Q.C. Luo, Y.Q. Zhai, et al., Chin. J. Chem. 40 (2022) 563–570. doi: 10.1002/cjoc.202100722
29. [29]
  A. Sarkar, G. Rajaraman, Chem. Sci. 11 (2020) 10324–10330. doi: 10.1039/d0sc03982a
30. [30]
  A. Swain, T. Sharma, G. Rajaraman, Chem. Commun. 59 (2023) 3206–3228. doi: 10.1039/d2cc06041h
31. [31]
  J.D. Rinehart, M. Fang, W.J. Evans, J.R. Long, Nat. Chem. 3 (2011) 538–542. doi: 10.1038/nchem.1063
32. [32]
  F. Liu, D.S. Krylov, L. Spree, et al., Nat. Commun. 8 (2017) 16098. doi: 10.1038/ncomms16098
33. [33]
  M. Guo, Y. Xu, J. Wu, L. Zhao, J. Tang, Dalton Trans. 46 (2017) 8252–8258. doi: 10.1039/C7DT01121K
34. [34]
  P.B. Jin, K.X. Yu, Y.Q. Zhai, et al., Chin. J. Chem. 39 (2021) 1635–1640. doi: 10.1002/cjoc.202100041
35. [35]
  F. Delano IV, F. Benner, S. Jang, S. Demir, Inorg. Chem. 62 (2023) 14604–14614. doi: 10.1021/acs.inorgchem.3c01724
36. [36]
  Y.S. Meng, J. Xiong, M.W. Yang, et al., Angew. Chem. Int. Ed. 59 (2020) 13037–13043. doi: 10.1002/anie.202004537
37. [37]
  M. Wang, X. Meng, N. Liu, et al., Chin. Chem. Lett. 34 (2023) 107995.
38. [38]
  D. Shao, P.P. Sahu, W.J. Tang, et al., Dalton Trans. 51 (2022) 18610–18621. doi: 10.1039/d2dt03046b
39. [39]
  P.B. Jin, Q.C. Luo, Y.Q. Zhai, et al., iScience 24 (2021) 102760.
40. [40]
  Y.C. Chen, M.L. Tong, Chem. Sci. 13 (2022) 8716–8726. doi: 10.1039/d2sc01532c
41. [41]
  Q.C. Luo, K.X. Yu, P.B. Jin, et al., Chin. J. Chem. 42 (2024) 391–396. doi: 10.1002/cjoc.202300491
42. [42]
  C. Jin, X.L. Li, Z. Liu, A. Mansikkamäki, J. Tang, Dalton Trans. 49 (2020) 10477–10485. doi: 10.1039/d0dt01926g
43. [43]
  W.J. Evans, J.W. Grate, I. Bloom, W.E. Hunter, J.L. Atwood, J. Am. Chem. Soc. 107 (1985) 405–409. doi: 10.1021/ja00288a021
44. [44]
  A.J. Wooles, O.J. Cooper, J. McMaster, et al., Organometallics 29 (2010) 2315–2321. doi: 10.1021/om100104s
45. [45]
  J. Corredoira-Vázquez, C. González-Barreira, M. Fondo, et al., Inorg. Chem. 61 (2022) 9946–9959. doi: 10.1021/acs.inorgchem.2c00773
46. [46]
  N.F. Chilton, R.P. Anderson, L.D. Turner, A. Soncini, K.S. Murray, J. Comput. Chem. 34 (2013) 1164–1175. doi: 10.1002/jcc.23234
47. [47]
  D. Reta, N.F. Chilton, Phys. Chem. Chem. Phys. 21 (2019) 23567–23575. doi: 10.1039/c9cp04301b
48. [48]
  I.F. Galván, M. Vacher, A. Alavi, et al., J. Chem. Theory Comput. 15 (2019) 5925–5964.
49. [49]
  L. Ungur, J.J. Le Roy, I. Korobkov, M. Murugesu, L.F. Chibotaru, Angew. Chem. Int. Ed. 53 (2014) 4413–4417. doi: 10.1002/anie.201310451
50. [50]
  Y. Wang, Q.C. Luo, Y.Q. Zhai, et al., Cryst. Growth Des. 22 (2022) 6398–6404. doi: 10.1021/acs.cgd.2c00892
51. [51]
  M.E. Lines, J. Chem. Phys. 55 (1971) 2977–2984.
52. [52]
  L.F. Chibotaru, L. Ungur, C. Aronica, et al., J. Am. Chem. Soc. 130 (2008) 12445–12455. doi: 10.1021/ja8029416
53. [53]
  L.F. Chibotaru, L. Ungur, A. Soncini, Angew. Chem. Int. Ed. 47 (2008) 4126–4129. doi: 10.1002/anie.200800283
54. [54]
  A. Lunghi, F. Totti, R. Sessoli, S. Sanvito, Nat. Commun. 8 (2017) 14620.
55. [55]
  Q.C. Luo, Y.Z. Zheng, Trends Chem. 5 (2023) 869–872.
56. [56]
  Y.S. Ding, K.X. Yu, D. Reta, et al., Nat. Commun. 9 (2018) 3134.
57. [57]
  L. Noodleman, J. Chem. Phys. 74 (1981) 5737–5743.
58. [58]
  L. Noodleman, E.R. Davidson, Chem. Phys. 109 (1986) 131–143.
59. [59]
  K. Yamaguchi, Y. Takahara, T. Fueno, Applied Quantum Chemistry, in: V.H. Smith, H.F. Schaefer, K. Morokuma (Eds.), Ab-Initio Molecular Orbital Studies of Structure and Reactivity of Transition Metal-OXO Compounds, Springer, Dordrecht, The Netherlands, 1986, pp. 155–184.
60. [60]
  Q.C. Luo, Y.Z. Zheng, Magnetochemistry 7 (2021) 107. doi: 10.3390/magnetochemistry7080107
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