Citation: Zhao-Bo Hu, Ling-Ao Gui, Long-He Li, Tong-Tong Xiao, Adam T. Hand, Pagnareach Tin, Mykhaylo Ozerov, Yan Peng, Zhongwen Ouyang, Zhenxing Wang, Zi-Ling Xue, You Song. Co^Ⅱ single-ion magnet and its multi-dimensional aggregations: Influence of the structural rigidity on magnetic relaxation process[J]. Chinese Chemical Letters, ;2025, 36(2): 109600. doi: 10.1016/j.cclet.2024.109600 shu

Co^Ⅱ single-ion magnet and its multi-dimensional aggregations: Influence of the structural rigidity on magnetic relaxation process

Zhao-Bo Hu ^{a, b, f, *,} ,
Ling-Ao Gui ^a ,
Long-He Li ^a ,
Tong-Tong Xiao ^c ,
Adam T. Hand ^d ,
Pagnareach Tin ^d ,
Mykhaylo Ozerov ^e ,
Yan Peng ^{a, f} ,
Zhongwen Ouyang ^c ,
Zhenxing Wang ^c ,
Zi-Ling Xue ^{d, *,} ,
You Song ^{b, *,}

a.
Chaotic Matter Science Research Center, Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China
b.
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
c.
Wuhan National High Magnetic Field Center & School of Physics, Huazhong University of Science and Technology, Wuhan 430074, China
d.
Department of Chemistry, University of Tennessee, Knoxville, TN 37996, United States
e.
National High Magnetic Field Laboratory, Florida State University, Tallahassee 32310, United States
f.
Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China

huzhaobo@smail.nju.edu.cn

xue@utk.edu

yousong@nju.edu.cn

Received Date: 20 December 2023
Revised Date: 21 January 2024
Accepted Date: 29 January 2024
Available Online: 4 February 2024

Figures(6)

Two Co^Ⅱ-based complexes, {[Co(dps)₂(N₃)₂]·H₂O} (1) and [Co(dps)₂(N₃)₂] (2), show a 1D chain and a 3D network, respectively. The central Co^Ⅱ ions in the complexes have the same coordination environment with the [Co(dps)₄(N₃)₂] unit. Although the differences in crystal parameters are nearly negligible, their magnetic properties are very different. AC susceptibility data show that 1 behaves as a typical field-induced single-ion magnet (SIM) with the out-of-phase (χ_M'') signals, while 2 shows ac signals of χ_M'' without peaks even under applied dc filed within our measurement window. Far-IR magneto-spectra (FIRMS) show strong spin-phonon couplings at 0 T in 2, likely making the magnetic relaxation in 2 fast, while the couplings are negligible in 1. Small spin-phonon coupling in 1 likely leads to slower magnetic relaxation, making 1 a SIM. The difference in the properties is due to the structural rigidity of 2 in its 3D network, leading to stronger spin-phonon coupling. Combined high-field EPR (HF-EPR) and FIRMS studies give spin-Hamiltonian parameters, including D = 64.0(9) cm^-1, E = 15.7(2) cm^-1 for 1 and D = 80.0(2) cm^-1, E = 19.0(1) cm^-1 for 2.
- Spin-phonon coupling,
- Slow magnetic relaxation,
- Structural rigidity,
- Co^Ⅱ compounds,
- Far-IR magneto-spectra
1. [1]
  W. Wernsdorfer, R. Sessoli, Science 284 (1999) 133.
2. [2]
  R. Sessoli, D. Gatteschi, A. Caneschi, M.A. Novak, Nature 365 (1993) 141.
3. [3]
  M.L. Kirk, D.A. Shultz, D.E. Stasiw, et al., J. Am. Chem. Soc. 135 (2013) 14713–14725. doi: 10.1021/ja405354x
4. [4]
  D.N. Woodruff, R.E.P. Winpenny, R.A. Layfield, Chem. Rev. 113 (2013) 5110–5148. doi: 10.1021/cr400018q
5. [5]
  A.J. Heinrich, W.D. Oliver, L.M.K. Vandersypen, et al., Nat. Nanotechnol. 16 (2021) 1318–1329. doi: 10.1038/s41565-021-00994-1
6. [6]
  T. Yamabayashi, M. Atzori, L. Tesi, et al., J. Am. Chem. Soc. 140 (2018) 12090–12101. doi: 10.1021/jacs.8b06733
7. [7]
  Q.C. Luo, N. Ge, Y.Q. Zhai, et al., Chin. Chem. Lett. 34 (2023) 107547.
8. [8]
  S. Li, Z.Z. Weng, L.P. Jiang, et al., Chin. Chem. Lett. 34 (2023) 107251.
9. [9]
  Y. Jiao, Y. Li, Y. Zhou, et al., Chin. Chem. Lett. 34 (2023) 109082.
10. [10]
  S. Yu, Z. Chen, H. Hu, et al., Dalton Trans. 48 (2019) 16679–16686. doi: 10.1039/c9dt03253c
11. [11]
  Z. Chen, S. Yu, R. Wang, et al., Dalton Trans. 48 (2019) 6627–6637. doi: 10.1039/c9dt00364a
12. [12]
  Z.B. Hu, Z.Y. Jing, M.M. Li, et al., Inorg. Chem. 57 (2018) 10761–10767. doi: 10.1021/acs.inorgchem.8b01389
13. [13]
  Z.B. Hu, X. Feng, J. Li, et al., Dalton Trans. 49 (2020) 2159–2167. doi: 10.1039/c9dt04403e
14. [14]
  J.L. Liu, Y.C. Chen, M.L. Tong, Chem. Soc. Rev. 47 (2018) 2431–2453. doi: 10.1039/c7cs00266a
15. [15]
  M. Briganti, E. Lucaccini, L. Chelazzi, et al., J. Am. Chem. Soc. 143 (2021) 8108–8115. doi: 10.1021/jacs.1c02502
16. [16]
  M. Feng, M.L. Tong, Chem. Eur. J. 24 (2018) 7574–7594. doi: 10.1002/chem.201705761
17. [17]
  Y.S. Meng, S.D. Jiang, B.W. Wang, S. Gao, Acc. Chem. Res. 49 (2016) 2381–2389. doi: 10.1021/acs.accounts.6b00222
18. [18]
  C.A. Gould, K.R. McClain, D. Reta, et al., Science 375 (2022) 198–202. doi: 10.1126/science.abl5470
19. [19]
  F.S. Guo, B.M. Day, Y.C. Chen, et al., Science 362 (2018) 1400–1403. doi: 10.1126/science.aav0652
20. [20]
  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
21. [21]
  L. Zhu, Y. Dong, B. Yin, P. Ma, D. Li, Dalton Trans. 50 (2021) 12607–12618. doi: 10.1039/d1dt00964h
22. [22]
  J. Wang, Q.W. Li, S.G. Wu, et al., Angew. Chem. Int. Ed. 60 (2021) 5299–5306. doi: 10.1002/anie.202014993
23. [23]
  S.K. Gupta, R. Murugavel, Chem. Commun. 54 (2018) 3685–3696. doi: 10.1039/c7cc09956h
24. [24]
  M. He, F.S. Guo, J. Tang, A. Mansikkamäki, R.A. Layfield, Chem. Commun. 57 (2021) 6396–6399. doi: 10.1039/d1cc02139g
25. [25]
  M. He, F.S. Guo, J. Tang, A. Mansikkamäki, R.A. Layfield, Chem. Sci. 11 (2020) 5745–5752. doi: 10.1039/d0sc02033h
26. [26]
  J.P. Durrant, J. Tang, A. Mansikkamäki, R.A. Layfield, Chem. Commun. 56 (2020) 4708–4711. doi: 10.1039/d0cc01722a
27. [27]
  M. Briganti, F. Santanni, L. Tesi, et al., J. Am. Chem. Soc. 143 (2021) 13633–13645. doi: 10.1021/jacs.1c05068
28. [28]
  A. Lunghi, F. Totti, R. Sessoli, S. Sanvito, Nat. Commun. 8 (2017) 14620.
29. [29]
  J. Li, S. J Xiong, C. Li, et al., CCS Chem. 2 (2020) 2548–2556. doi: 10.3390/app10072548
30. [30]
  Q. Chen, F. Ma, Y.S. Meng, et al., Inorg. Chem. 55 (2016) 12904–12911. doi: 10.1021/acs.inorgchem.6b02276
31. [31]
  Q. Chen, J. Li, Y.S. Meng, et al., Inorg. Chem. 55 (2016) 7980–7987. doi: 10.1021/acs.inorgchem.6b01014
32. [32]
  Q. Chen, Y.S. Meng, Y.Q. Zhang, et al., Chem. Commun. 50 (2014) 10434–10437.
33. [33]
  C. Li, J. Sun, M. Yang, et al., Cryst. Growth Des. 16 (2016) 7155–7162. doi: 10.1021/acs.cgd.6b01369
34. [34]
  Y. Rechkemmer, F.D. Breitgoff, M. van der Meer, et al., Nat. Comm. 7 (2016) 10467.
35. [35]
  D.H. Moseley, S.E. Stavretis, K. Thirunavukkuarasu, et al., Nat. Comm. 9 (2018) 2572.
36. [36]
  D.H. Moseley, S.E. Stavretis, Z. Zhu, et al., Inorg. Chem. 59 (2020) 5218–5230. doi: 10.1021/acs.inorgchem.0c00523
37. [37]
  A.N. Bone, C.N. Widener, D.H. Moseley, et al., Chem. Eur. J. 27 (2021) 11110–11125. doi: 10.1002/chem.202100705
38. [38]
  J.G.C. Kragskow, J. Marbey, C.D. Buch, et al., Nat. Comm. 13 (2022) 825.
39. [39]
  D.H. Moseley, Z. Liu, A.N. Bone, et al., Inorg. Chem. 61 (2022) 17123–17136. doi: 10.1021/acs.inorgchem.2c02604
40. [40]
  F. Liedy, J. Eng, R. McNab, et al., Nat. Chem. 12 (2020) 452–458. doi: 10.1038/s41557-020-0431-6
41. [41]
  X.Z. Luo, S. Xin, J.H. Yu, J Chin, Inorg. Chem. 26 (2010) 1299–1302.
42. [42]
  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
43. [43]
  The SPIN program was developed by Dr. Andrzej Ozarowski to "simulates powder or single-crystal EPR spectra for spin states with ½ < S < 5. " It is free at https://nationalmaglab.org/user-facilities/emr/software/.
44. [44]
  L. Chen, J. Wang, J.M. Wei, et al., J. Am. Chem. Soc. 136 (2014) 12213–12216. doi: 10.1021/ja5051605
45. [45]
  A.N. Bone, S.E. Stavretis, J. Krzystek, et al., Polyhedron 184 (2020) 114488.
46. [46]
  C.N. Widener, A.N. Bone, M. Ozerov, et al., Chin. J. Inorg. Chem. 35 (2020) 1149–1156.
47. [47]
  S.E. Stavretis, D.H. Moseley, F. Fei, et al., Chem. Eur. J. 25 (2019) 15846–15857. doi: 10.1002/chem.201903635
48. [48]
  P. Tin, S.E. Stavretis, M. Ozerov, et al., Appl. Mang. Reson. 51 (2020) 1411–1432. doi: 10.1007/s00723-020-01236-8
49. [49]
  J. Vallejo, M. Viciano-Chumillas, F. Lloret, et al., Inorg. Chem. 58 (2019) 15726–15740. doi: 10.1021/acs.inorgchem.9b01719
50. [50]
  P. Tin, A.N. Bone, N.N. Bui, et al., J. Phys. Chem. B 126 (2022) 13268–13283. doi: 10.1021/acs.jpcc.2c03083
51. [51]
  Y.N. Guo, G.F. Xu, Y. Guo, J. Tang, Dalton Trans. 40 (2011) 9953–9963. doi: 10.1039/c1dt10474h
52. [52]
  A. Albino, S. Benci, L. Tesi, et al., Inorg. Chem. 58 (2019) 10260–10268. doi: 10.1021/acs.inorgchem.9b01407
53. [53]
  F. Santanni, A. Albino, M. Atzori, et al., Inorg. Chem. 60 (2021) 140–151. doi: 10.1021/acs.inorgchem.0c02573
54. [54]
  A. Lunghi, S. Sanvito, J. Chem. Phys. 153 (2020) 174113.
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CoⅡ single-ion magnet and its multi-dimensional aggregations: Influence of the structural rigidity on magnetic relaxation process

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Co^Ⅱ single-ion magnet and its multi-dimensional aggregations: Influence of the structural rigidity on magnetic relaxation process