Citation: Xiao-Qin WEI, Feng-Ying ZHANG, Wan-Xi LI, Xin-Yi WANG, Ai-Hua ZHANG, Yu-Fang LIU. Synthesis and Slow Magnetic Relaxation of a Disc-like Dysprosium Cluster[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(7): 1382-1390. doi: 10.11862/CJIC.2022.141 shu

Synthesis and Slow Magnetic Relaxation of a Disc-like Dysprosium Cluster

1.
Shanxi Province Collaborative Innovation Center for Light Materials Modification and Application, Department of Material Science and Engineering, Jinzhong University, Jinzhong, Shanxi 030619, China
2.
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
3.
Department of Chemistry and Chemical Engineering, Jinzhong University, Jinzhong, Shanxi 030619, China

Corresponding author: Xiao-Qin WEI, weixiaoqin@jzxy.edu.cn Xin-Yi WANG, wangxy66@nju.edu.cn
Received Date: 29 March 2022
Revised Date: 4 May 2022

Figures(10)

By using rare earth salt of DyCl₃·6H₂O, a bidentate ligand of tmphen and the block of[Mo^Ⅲ(CN)₇]^4-, a dysprosium heptanuclear cluster was self-assembled with the formula of[Dy^Ⅲ₇(tmphen)₁₂O₆(OH)₆Cl₂] [Mo^Ⅵ(tmphen) O(CN)₃]₆Cl₇·66H₂O (1, tmphen=3, 4, 7, 8-tetramethyl-1, 10-phenanthroline), which was characterized structurally and magnetically. The crystal structure shows that compound 1 is dominated by a disc-like structure of dysprosium heptanuclear. The[Mo^Ⅲ(CN)₇]^4- block was oxidized and decomposed, forming[Mo^Ⅵ(tmphen) O (CN)₃]⁺ cations free in the lattice. Besides, weak π-π interactions are found between aromatic rings of tmphen. The direct-current (dc) magnetic susceptibility indicated this compound had no hysteresis loop at low temperatures due to the existence of the quantum tunneling relaxation path. The alternating current (ac) magnetic susceptibility, however, illustrated that the compound exhibited slow magnetic relaxation under zero field, showing the properties of a single-molecule magnet, with an effective barrier of 51.6 K (35.8 cm^-1, τ₀=17 μs).
- dysprosium,
- polynuclear clusters,
- magnetic anisotropy,
- single-molecule magnets,
- magnetic relaxation
1. [1]
  Miller J S, Gatteschi D. Molecule-Based Magnets[J]. Chem. Soc. Rev., 2011,40:3065-3066. doi: 10.1039/c1cs90019f
2. [2]
  Leuenberger M N, Loss D. Quantum Computing in Molecular Magnets[J]. Nature, 2001,410:789-793. doi: 10.1038/35071024
3. [3]
  Bogani L, Wernsdorfer W. Molecular Spintronics Using Single-Molecule Magnets[J]. Nat. Mater., 2008,7(3):179-186. doi: 10.1038/nmat2133
4. [4]
  Candini A, Klyatskaya S, Ruben M, Wernsdorfer W, Affronte M. Graphene Spintronic Devices with Molecular Nanomagnets[J]. Nano Lett., 2011,11(7):2634-2639. doi: 10.1021/nl2006142
5. [5]
  Sessoli R, Gatteschi D, Caneschi A, Novak M A. High-Spin Molecules: [Mn₁₂O₁₂(O₂CR)₁₆(H₂O)₄][J]. Nature, 1993,365(6442):141-143. doi: 10.1038/365141a0
6. [6]
  Shao D, Wang X Y. Development of Single-Molecule Magnets[J]. Chinese J. Chem., 2020,38(9):1005-1018. doi: 10.1002/cjoc.202000090
7. [7]
  Sessoli R, Powell A K. Strategies towards Single Molecule Magnets Based on Lanthanide Ions[J]. Coord. Chem. Rev., 2009,253(19):2328-2341.
8. [8]
  Ishikawa N, Sugita M, Ishikawa T, Koshihara S, Kaizu Y. Lanthanide Double-Decker Complexes Functioning as Magnets at the Single-Molecular Level[J]. J. Am. Chem. Soc., 2003,125(29):8694-8695. doi: 10.1021/ja029629n
9. [9]
  Gómez-Coca S, Aravena D, Morales R, Ruiz E. Large Magnetic Anisotropy in Mononuclear Metal Complexes[J]. Coord. Chem. Rev., 2015,289:379-392.
10. [10]
  Woodruff D N, Winpenny R E P, Layfield R A. Lanthanide Single-Molecule Magnets[J]. Chem. Rev., 2013,113(7):5110-5148. doi: 10.1021/cr400018q
11. [11]
  Liu J L, Chen Y C, Tong M L. Symmetry Strategies for High Performance Lanthanide-Based Single-Molecule Magnets[J]. Chem. Soc. Rev., 2018,47(7):2431-2453. doi: 10.1039/C7CS00266A
12. [12]
  Rinehart J D, Long J R. Exploiting Single-Ion Anisotropy in the Design of f-Element Single-Molecule Magnets[J]. Chem. Sci., 2011,2(11):2078-2085. doi: 10.1039/c1sc00513h
13. [13]
  Dey A, Kalita P, Chandrasekhar V. Lanthanide(Ⅲ)-Based Single-Ion Magnets[J]. ACS Omega, 2018,3(8):9462-9475. doi: 10.1021/acsomega.8b01204
14. [14]
  REN M, ZHENG L M. Lanthanide-Based Single Molecule Magnets[J]. Acta Chim. Sinica, 2015,73(11):1091-1113.
15. [15]
  Li H Q, Sun Y C, Shi L, Chen F L, Shen F X, Zhao Y, Wang X Y. Modulating the Structures and Magnetic Properties of Dy (Ⅲ) Single-Molecule Magnets through Acid-Base Regulation[J]. Inorg. Chem., 2022,61(4):2272-2283. doi: 10.1021/acs.inorgchem.1c03639
16. [16]
  Goodwin C A P, Ortu F, Reta D, Chilton N F, Mills D P. Molecular Magnetic Hysteresis at 60 Kelvin in Dysprosocenium[J]. Nature, 2017,548(7668):439-442. doi: 10.1038/nature23447
17. [17]
  Guo F S, Day B M, Chen Y C, Tong M L, Mansikkamäki A, Layfield R A. Magnetic Hysteresis up to 80 Kelvin in a Dysprosium Metallocene Single-Molecule Magnet[J]. Science, 2018,362(6421):1400-1403. doi: 10.1126/science.aav0652
18. [18]
  Pointillart F, Cador O, Le Guennic B, Ouahab L. Uncommon Lanthanide Ions in Purely 4f Single Molecule Magnets[J]. Coord. Chem. Rev., 2017,346:150-175. doi: 10.1016/j.ccr.2016.12.017
19. [19]
  Ashebr T G, Li H, Ying X, Li X L, Zhao C, Liu S, Tang J K. Emerging Trends on Designing High-Performance Dysprosium (Ⅲ) Single-Molecule Magnets[J]. ACS Mater. Lett., 2022,4(2):307-319. doi: 10.1021/acsmaterialslett.1c00765
20. [20]
  Liu K, Shi W, Cheng P. Toward Heterometallic Single-Molecule Magnets: Synthetic Strategy, Structures and Properties of 3d-4f Discrete Complexes[J]. Coord. Chem. Rev., 2015,289:74-122.
21. [21]
  Demir S, Jeon I R, Long J R, Harris T D. Radical Ligand-Containing Single-Molecule Magnets[J]. Coord. Chem. Rev., 2015,289:149-176.
22. [22]
  Mironov V S, Chibotaru L F, Ceulemans A. Mechanism of a Strongly Anisotropic Mo^Ⅲ-CN-Mn^Ⅱ Spin-Spin Coupling in Molecular Magnets Based on the [Mo(CN)₇]^4- Heptacyanometalate: A New Strategy for Single-Molecule Magnets with High Blocking Temperatures[J]. J. Am. Chem. Soc., 2003,125(32):9750-9760. doi: 10.1021/ja029518o
23. [23]
  Qian K, Huang X C, Zhou C, You X Z, Wang X Y, Dunbar K R. A Single-Molecule Magnet Based on Heptacyanomolybdate with the Highest Energy Barrier for a Cyanide Compound[J]. J. Am. Chem. Soc., 2013,135(36):13302-13305. doi: 10.1021/ja4067833
24. [24]
  Shi L, Shao D, Wei X Q, Dunbar K R, Wang X Y. Enhanced Single-Chain Magnet Behavior via Anisotropic Exchange in a Cyano-Bridged Mo^Ⅲ-Mn^Ⅱ Chain[J]. Angew. Chem. In. Ed., 2020,59(26):10379-10384. doi: 10.1002/anie.202001706
25. [25]
  Wu D Q, Shao D, Wei X Q, Shen F X, Shi L, Kempe D, Zhang Y Z, Dunbar K R, Wang X Y. Enhanced Single-Chain Magnet Behavior via Anisotropic Exchange in a Cyano-Bridged Mo^Ⅲ-Mn^Ⅱ Chain[J]. J. Am. Chem. Soc., 2017,139(34):11714-11717. doi: 10.1021/jacs.7b07008
26. [26]
  Wei X Q, Qian K, Wei H Y, Wang X Y. A One-Dimensional Magnet Based on[Mo^Ⅲ(CN)₇]^4-[J]. Inorg. Chem., 2016,55(11):5107-5109. doi: 10.1021/acs.inorgchem.6b00787
27. [27]
  Wei X Q, Wang K J, Wu D Q, Shao D, Shi L, Shen F X, Wei H Y, Wang X Y. Two Three-Dimensional[Mo^Ⅲ(CN)₇]^4--Based Magnets Showing New Topologies and Ferrimagnetic Ordering below 80 K[J]. Dalton Trans., 2019,48(24):8843-8853. doi: 10.1039/C9DT01290G
28. [28]
  Young R C. A Complex Cyanide of Trivalent Molybdenum[J]. J. Am.Chem. Soc., 1932,54(4):1402-1405. doi: 10.1021/ja01343a018
29. [29]
  CrysAlis Pro, Rigaku Oxford Diffraction Ltd., Yarnton, England, 2021.
30. [30]
  Dolomanov O V, Bourhis L J, Gildea R J, Howard J A K, Puschmann H. OLEX2:A Complete Structure Solution, Refinement and Analysis Program[J]. J. Appl. Crystallogr., 2009,42(2):339-341. doi: 10.1107/S0021889808042726
31. [31]
  Sheldrick G M. SHELXT-Integrated Space-Group and Crystal-Structure Determination[J]. Acta Crystallogr. Sect. A, 2015,A71(1):3-8.
32. [32]
  Llunell M, Casanova D, Cirera J, Alemany P, Alvarez S. SHAPE Version 2.1, University of Barcelona, Spain, 2013.
33. [33]
  Altermatt D, Brown I D. The Automatic Searching for Chemical Bonds in Inorganic Crystal Structures[J]. Acta Crystallogr. Sect. B, 1985,B41:240-244.
34. [34]
  Brese N E, O'Keeffe M. Bond-Valence Parameters for Solids[J]. Acta Crystallogr. Sect. B, 1991,47:192-197. doi: 10.1107/S0108768190011041
35. [35]
  Brown I D. Recent Developments in the Methods and Applications of the Bond Valence Model[J]. Chem. Rev., 2009,109(12):6858-6919. doi: 10.1021/cr900053k
36. [36]
  Sharples J W, Zheng Y Z, Tuna F, McInnes E J L, Collison D. Lanthanide Discs Chill Well and Relax Slowly[J]. Chem. Commun., 2011,47(27):7650-7652. doi: 10.1039/c1cc12252e
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