Citation: Jiajia Zhuang, Chunyu Cui, Changjiang Li, Gang Luo, Jiaping Tong, Di Sun. Counter-ion effect to the Ising-type magnetic anisotropy and magnetic relaxation in trigonal bipyramidal Co(Ⅱ) complexes[J]. Chinese Chemical Letters, ;2025, 36(7): 110091. doi: 10.1016/j.cclet.2024.110091 shu

Counter-ion effect to the Ising-type magnetic anisotropy and magnetic relaxation in trigonal bipyramidal Co(Ⅱ) complexes

Jiajia Zhuang ^a ,
Chunyu Cui ^b ,
Changjiang Li ^a ,
Gang Luo ^a ,
Jiaping Tong ^{a, *,} ,
Di Sun ^{c, *,}

a.
Laboratory of Physicochemical Analysis, Training Base, Army Logistics Academy, Chongqing 400041, China
b.
Department of Physics, College of Basic Medical Science, Army Medical University, Chongqing 400038, China
c.
Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Ji'nan 250100, China

jiapingtong@hotmail.com

dsun@sdu.edu.cn

Received Date: 11 April 2024
Revised Date: 16 May 2024
Accepted Date: 4 June 2024
Available Online: 5 June 2024

Figures(8)

A larger counter-ion could change the environment of trigonal bipyramidal cobalt(Ⅱ) to some extent, diluting the cobalt-containing complex and slowing their magnetic relaxation. Considering this observation, we used a sulfur organic ligand NS₃^tBu to obtain two trigonal bipyramidal Co(Ⅱ) complexes, namely, [Co(NS₃^tBu)Cl]Y, Y = PF₆^– (1), ClO₄^– (2). The resulting compound 1 (with a larger counter-ion PF₆^–) exhibits a longer relaxation time in comparison to compound 2 prepared with the smaller counter-ion ClO₄^–, even though the presence of weak rhombicity decreases the energy barrier and speeds up the relaxation of the magnetization for the two compounds. Concurrently, we demonstrate that compound 1 has smaller effective energy barrier and displays slower magnetic relaxation rather than compound 2. A smaller dc magnetic field could almost suppress all the quantum tunneling of magnetization (QTM), direct and Raman processes in compound 1, but not in compound 2, which presents all the Orbach, QTM, direct and Raman processes.
- Magnetic property,
- Molecular magnet,
- Single ion magnet,
- Cobalt(Ⅱ),
- Counter-ion effect
1. [1]
  A. Caneschi, D. Gatteschi, R. Sessoli, et al., J. Am. Chem. Soc. 113 (1991) 5873–5874. doi: 10.1021/ja00015a057
2. [2]
  R. Sessoli, D. Gatteschi, A. Caneschi, M.A. Novak, Nature 365 (1993) 141–143.
3. [3]
  F. Liu, N. Yang, L.T. Zhang, et al., Food Biosci. 53 (2023) 102667–102800.
4. [4]
  F. Shao, J.J. Zhuang, M.G. Chen, et al., Dalton Trans. 47 (2018) 16850–16854. doi: 10.1039/c8dt04153a
5. [5]
  F.S. Guo, B.M. Day, Y.C. Chen, et al., Science 362 (2018) 1400–1403. doi: 10.1126/science.aav0652
6. [6]
  K. Choroba, J. Palion-Gazda, B. Machura, et al., Inorg. Chem. 63 (2024) 1068–1082. doi: 10.1021/acs.inorgchem.3c03405
7. [7]
  P.C. Bunting, M. Atanasov, E. Damgaard-Møller, et al., Science 362 (2018) 7319.
8. [8]
  R. Luo, C.Z. Xie, M.G. Chen, et al., Chin. J. Chem. 41 (2023) 3662–3668. doi: 10.1002/cjoc.202300432
9. [9]
  Z. Zhu, M. Guo, X.L. Li, J. Tang, Coord. Chem. Rev. 378 (2019) 350–364.
10. [10]
  M. Urdampilleta, S. Klyatskaya, J.P. Cleuziou, M. Ruben, W. Wernsdorfer, Nat. Mater. 10 (2011) 502–506. doi: 10.1038/nmat3050
11. [11]
  G. Lococciolo, S.K. Gupta, S. Dechert, et al., Inorg. Chem. 63 (2024) 5652–5663. doi: 10.1021/acs.inorgchem.4c00054
12. [12]
  C.A.P. Goodwin, F. Ortu, D. Reta, N.F. Chilton, D.P. Mills, Nature 548 (2017) 439. doi: 10.1038/nature23447
13. [13]
  S.K. Gupta, H.H. Nielsen, A.M. Thiel, et al., JACS Au 3 (2023) 429–440. doi: 10.1021/jacsau.2c00575
14. [14]
  S. Thiele, F. Balestro, R. Ballou, et al., Science 344 (2014) 1135. doi: 10.1126/science.1249802
15. [15]
  P.K. Sahu, R. Kharel, S. Shome, S. Goswami, S. Konar, Coord. Chem. Rev. 475 (2023) 214871.
16. [16]
  R. Vincent, S. Klyatskaya, M. Ruben, W. Wernsdorfer, F. Balestro, Nature 488 (2012) 357–360. doi: 10.1038/nature11341
17. [17]
  L. Bogani, W. Wernsdorfer, Nat. Mater. 7 (2008) 179–186. doi: 10.1038/nmat2133
18. [18]
  M. Shiddiq, D. Komijani, Y. Duan, et al., Nature 531 (2016) 348–351. doi: 10.1038/nature16984
19. [19]
  F. Shao, B. Cahier, N. Guihery, et al., Chem. Commun. 51 (2015) 16475–16478.
20. [20]
  A.M. Ako, I.J. Hewitt, V. Mereacre, et al., Angew. Chem. 118 (2006) 5048–5051. doi: 10.1002/ange.200601467
21. [21]
  V.E. Campbell, H. Bolvin, E. Rivière, et al., Inorg. Chem. 53 (2014) 2598–2605. doi: 10.1021/ic402950j
22. [22]
  Y.S. Ding, K.X. Yu, D. Reta, et al., Nat. Commun. 9 (2018) 3134.
23. [23]
  R. Ruamps, L.J. Batchelor, R. Guillot, et al., Chem. Sci. 5 (2014) 3418–3424.
24. [24]
  R. Ruamps, R. Maurice, L. Batchelor, et al., J. Am. Chem. Soc. 135 (2013) 3017–3026. doi: 10.1021/ja308146e
25. [25]
  J.M. Zadrozny, D.J. Xiao, M. Atanasov, et al., Nat. Chem. 5 (2013) 577–581. doi: 10.1038/nchem.1630
26. [26]
  J.M. Zadrozny, J. Liu, N.A. Piro, et al., Chem. Commun. 48 (2012) 3927–3929. doi: 10.1039/c2cc16430b
27. [27]
  D. Schweinfurth, M.G. Sommer, M. Atanasov, et al., J. Am. Chem. Soc. 137 (2015) 1993–2005. doi: 10.1021/ja512232f
28. [28]
  F. El-Khatib, B. Cahier, F. Shao, et al., Inorg. Chem. 56 (2017) 4601–4608. doi: 10.1021/acs.inorgchem.7b00205
29. [29]
  M. He, F.S. Guo, J. Tang, A. Mansikkamäki, R.A. Layfield, Chem. Commun. 57 (2021) 6396–6399. doi: 10.1039/d1cc02139g
30. [30]
  A. Lunghi, F. Totti, R. Sessoli, S. Sanvito, Nat. Commun. 8 (2017) 14620.
31. [31]
  G.A. Timco, S. Carretta, F. Troiani, et al., Nat. Nano 4 (2009) 173–178. doi: 10.1038/nnano.2008.404
32. [32]
  F. Shao, B. Cahier, E. Rivière, et al., Inorg. Chem. 56 (2017) 1104–1111. doi: 10.1021/acs.inorgchem.6b01966
33. [33]
  F. Shao, Doctoral Thesis: Engineering Magnetic Anisotropy in Mononulear Cobalt(Ⅱ) Complexes and Lanthanide-based Metallacrowns, Université Paris–Sud, Université Paris-Saclay, Paris, 2017.
34. [34]
  K.S. Cole, R.H. Cole, J. Chem. Phys. 9 (1941) 341–351. doi: 10.1063/1.1750906
35. [35]
  M. Perovic, V. Kusigerski, V. Spasojevic, et al., J. Phys. D: Appl. Phys. 46 (2013) 165001. doi: 10.1088/0022-3727/46/16/165001
36. [36]
  V.V. Novikov, A.A. Pavlov, Y.V. Nelyubina, et al., J. Am. Chem. Soc. 137 (2015) 9792–9795. doi: 10.1021/jacs.5b05739
37. [37]
  J.M. Zadrozny, M. Atanasov, A.M. Bryan, et al., Chem. Sci. 4 (2013) 125–138.
38. [38]
  Y. Rechkemmer, F.D. Breitgoff, M. van der Meer, et al., Nat. Commun. 7 (2016) 10467.
39. [39]
  B. Cahier, R. Maurice, H. Bolvin, T. Mallah, N. Guihéry, Magnetochemistry 2 (2016) 31. doi: 10.3390/magnetochemistry2030031
40. [40]
  F.E. Mabbs, D. Collison, Electron Paramagnetic Resonance of d Transition Metal Compounds, Elsevier, The Netherlands, 2013.
41. [41]
  J.N. Rebilly, G. Charron, E. Rivière, et al., Chem. Eur. J. 14 (2008) 1169–1177. doi: 10.1002/chem.200701243
1. [1]
  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. Chinese Chemical Letters, 2025, 36(2): 109600-. doi: 10.1016/j.cclet.2024.109600
2. [2]
  Shuyan ZHAO . Field-induced Co^Ⅱ single-ion magnet with pentagonal bipyramidal configuration. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1583-1591. doi: 10.11862/CJIC.20240231
3. [3]
  Xiaoling WANG , Hongwu ZHANG , Daofu LIU . Synthesis, structure, and magnetic property of a cobalt(Ⅱ) complex based on pyridyl-substituted imino nitroxide radical. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 407-412. doi: 10.11862/CJIC.20240214
4. [4]
  Yinling HOU , Jia JI , Hong YU , Xiaoyun BIAN , Xiaofen GUAN , Jing QIU , Shuyi REN , Ming FANG . A rhombic Dy₄-based complex showing remarkable single-molecule magnet behavior. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 605-612. doi: 10.11862/CJIC.20240251
5. [5]
  Dan Shao , Yujing Lyu , Chengyuan Liu , Hao Wang , Ning Ma , Hao Xu , Wei Yan , Xiaohua Jia , Haojie Song . Attracting magnetic BDD particles onto Ti/RuO₂-IrO₂ by using a magnet: A novel 2.5-dimensional electrode for electrochemical oxidation wastewater treatment. Chinese Chemical Letters, 2025, 36(6): 110641-. doi: 10.1016/j.cclet.2024.110641
6. [6]
  Shimei Wu , Yining Li , Lantao Chen , Yufei Zhang , Lingxing Zeng , Haosen Fan . Hexapod cobalt phosphosulfide nanorods encapsulating into multiple hetero-atom doped carbon frameworks for advanced sodium/potassium ion battery anodes. Chinese Chemical Letters, 2025, 36(4): 109796-. doi: 10.1016/j.cclet.2024.109796
7. [7]
  Jun-Jie Fang , Yun-Peng Xie , Xing Lu . Organooxotin and cobalt/manganese heterometallic nanoclusters exhibiting single-molecule magnetism. Chinese Journal of Structural Chemistry, 2025, 44(4): 100515-100515. doi: 10.1016/j.cjsc.2025.100515
8. [8]
  Shuangying Li , Qingxiang Zhou , Zhi Li , Menghua Liu , Yanhui Li . Sensitive measurement of silver ions in environmental water samples integrating magnetic ion-imprinted solid phase extraction and carbon dot fluorescent sensor. Chinese Chemical Letters, 2024, 35(5): 108693-. doi: 10.1016/j.cclet.2023.108693
9. [9]
  Brandon Bishop , Shaofeng Huang , Hongxuan Chen , Haijia Yu , Hai Long , Jingshi Shen , Wei Zhang . Artificial transmembrane channel constructed from shape-persistent covalent organic molecular cages capable of ion and small molecule transport. Chinese Chemical Letters, 2024, 35(11): 109966-. doi: 10.1016/j.cclet.2024.109966
10. [10]
  Xiao-Fang Lv , Xiao-Yun Ran , Yu Zhao , Rui-Rui Zhang , Li-Na Zhang , Jing Shi , Ji-Xuan Xu , Qing-Quan Kong , Xiao-Qi Yu , Kun Li . Combing NIR-Ⅱ molecular dye with magnetic nanoparticles for enhanced photothermal theranostics with a 95.6% photothermal conversion efficiency. Chinese Chemical Letters, 2025, 36(4): 110027-. doi: 10.1016/j.cclet.2024.110027
11. [11]
  Xuanyang Jin , Xincheng Guo , Siyang Dong , Shilan Li , Shengdong Jin , Peng Xia , Shengjun Lu , Yufei Zhang , Haosen Fan . Synergistic regulation of polysulfides shuttle effect and lithium dendrites from cobalt-molybdenum bimetallic carbides (Co-Mo-C) heterostructure for robust Li-S batteries. Chinese Chemical Letters, 2025, 36(7): 110604-. doi: 10.1016/j.cclet.2024.110604
12. [12]
  Yan Cheng , Hua-Peng Ruan , Yan Peng , Longhe Li , Zhenqiang Xie , Lang Liu , Shiyong Zhang , Hengyun Ye , Zhao-Bo Hu . Magnetic, dielectric and luminescence synergetic switchable effects in molecular material [Et₃NCH₂Cl]₂[MnBr₄]. Chinese Chemical Letters, 2024, 35(4): 108554-. doi: 10.1016/j.cclet.2023.108554
13. [13]
  Xingang Kong , Yabei Su , Cuijuan Xing , Weijie Cheng , Jianfeng Huang , Lifeng Zhang , Haibo Ouyang , Qi Feng . Facile synthesis of porous TiO₂/SnO₂ nanocomposite as lithium ion battery anode with enhanced cycling stability via nanoconfinement effect. Chinese Chemical Letters, 2024, 35(11): 109428-. doi: 10.1016/j.cclet.2023.109428
14. [14]
  Yuanjin Chen , Xianghui Shi , Dajiang Huang , Junnian Wei , Zhenfeng Xi . Synthesis and reactivity of cobalt dinitrogen complex supported by nonsymmetrical pincer ligand. Chinese Chemical Letters, 2024, 35(7): 109292-. doi: 10.1016/j.cclet.2023.109292
15. [15]
  Minghui Zhang , Na Zhang , Qian Zhao , Chao Wang , Alexander Steiner , Jianliang Xiao , Weijun Tang . Cobalt pincer complex-catalyzed highly enantioselective hydrogenation of quinoxalines. Chinese Chemical Letters, 2025, 36(4): 110081-. doi: 10.1016/j.cclet.2024.110081
16. [16]
  Jiayi Guo , Liangxiong Ling , Qinwei Lu , Yi Zhou , Xubiao Luo , Yanbo Zhou . Degradation of chloroxylenol by CoS_x activated peroxomonosulfate: Role of cobalt-sulfur ratio. Chinese Chemical Letters, 2025, 36(4): 110380-. doi: 10.1016/j.cclet.2024.110380
17. [17]
  Qing Li , Fangyu Fu , Mengyun Zhao , Yeqin Feng , Manzhou Chi , Zichen Zhao , Hongjin Lv , Guo-Yu Yang . Asymmetrically anchoring silver alkynyl cluster to the cobalt-containing polyoxometalate. Chinese Chemical Letters, 2025, 36(7): 110090-. doi: 10.1016/j.cclet.2024.110090
18. [18]
  Zheyi Li , Xiaoyang Liang , Zitong Qiu , Zimeng Liu , Siyu Wang , Yue Zhou , Nan Li . Ion-interferential cell cycle arrest for melanoma treatment based on magnetocaloric bimetallic-ion sustained release hydrogel. Chinese Chemical Letters, 2024, 35(11): 109592-. doi: 10.1016/j.cclet.2024.109592
19. [19]
  Yang Li , Xiaoxu Liu , Tianyi Ji , Man Zhang , Xueru Yan , Mengjie Yao , Dawei Sheng , Shaodong Li , Peipei Ren , Zexiang Shen . Potassium ion doped manganese oxide nanoscrolls enhanced the performance of aqueous zinc-ion batteries. Chinese Chemical Letters, 2025, 36(1): 109551-. doi: 10.1016/j.cclet.2024.109551
20. [20]
  Ruike Hu , Kangmin Wang , Junxiang Liu , Jingxian Zhang , Guoliang Yang , Liqiu Wan , Bijin Li . Extended π-conjugated systems by external ligand-assisted C−H olefination of heterocycles: Facile access to single-molecular white-light-emitting and NIR fluorescence materials. Chinese Chemical Letters, 2025, 36(4): 110113-. doi: 10.1016/j.cclet.2024.110113

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(4)
HTML views(1)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142