Citation: Wen-Jie JI, Cheng-Cai XIA, Xin-Yu ZHANG, Xin-Yi WANG. Anionic Modification of the Cu-Tb Single-Molecule Magnets Based on the Compartmental Schiff-Base Ligand[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(6): 1199-1208. doi: 10.11862/CJIC.2022.117 shu

Anionic Modification of the Cu-Tb Single-Molecule Magnets Based on the Compartmental Schiff-Base Ligand

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China

Corresponding author: Xin-Yi WANG, wangxy66@nju.edu.cn
Received Date: 13 April 2022
Revised Date: 2 May 2022

Figures(7)

By using different anions, three Cu-Tb metal complexes, namely [Cu₂(vanophen)₂TbCl₂(MeOH)₂]Cl· 3MeOH (1), [Cu₂(vanophen)₂TbCl₂(MeOH)₂](TCNQ)_1.5·2MeOH (2), and [Cu₂(vanophen)₂Tb₂(N₃)₆]·2MeOH (3), based on the compartmental Schiff-base ligand H₂vanophen (H₂vanophen=N, N′-bis(2-oxy-3-methoxybenzylidene)-1, 2-phenylenediamine, TCNQ=7, 7, 8, 8-tetracyanoquinodimethane) have been synthesized and characterized structurally and magnetically. Except for the different charge-balancing anions, complexes 1 and 2 have a very similar trinuclear [CuTbCu] structure, where the Cu(Ⅱ) ions are in the [N₂O₄] coordination pockets of the ligands, while the Tb(Ⅲ) ion is coordinated by all or some of the oxygen atoms from the [O₄] pocket of the ligands. The charge-balancing anion is a Cl^- ion in 1, while the positive charge is balanced by one TCNQ^-0.5 radical and a half of the TCNQ^- radical in 2. As for complex 3, it has a tetranuclear [CuTb]₂ structure, where two [CuTb] units are bridged by end-end and end-on azides. Magnetic studies revealed that both 1 and 2 are field-induced SMMs while 3 is a zero-field SMM. The energy barriers of 1 and 3 were estimated to be (11.1±0.3) cm^-1 and (20.2±0.3) cm^-1, respectively. As for complex 2, its energy barrier was lower than that of 1, which might be due to the weak magnetic interaction between the [CuTbCu] unit and the paramagnetic radical anions.
- single-molecule magnet,
- compartmental Schiff-base ligand,
- anionic modification,
- 3d-4f complexes
1. [1]
  (a) Andoni Z L, Jose M S, Enrique C. Single-Molecule Magnets: From Mn12-ac to Dysprosium Metallocenes, a Travel in Time. Coord. Chem. Rev., 2021, 441: 3984-4020
  (b)Shao D, Wang X Y. Development of Single-Molecule Magnets. Chin. J. Chem., 2020, 38: 1005-1018
2. [2]
  Zhu Z, Guo M, Li X L, Tang J. Molecular Magnetism of Lanthanide: Advances and Perspectives[J]. Coord. Chem. Rev., 2019,378:350-364. doi: 10.1016/j.ccr.2017.10.030
3. [3]
  Ding X L, Zhai Y Q, Han T, Chen W P, Ding Y S, Zheng Y Z. A Local D_4h Symetric Dysprosiun(Ⅲ) Single-Molecule Magnet with an Energy Barrier Exceeding 2 000 K[J]. Chem. Eur. J., 2021,27:2623-2627. doi: 10.1002/chem.202003931
4. [4]
  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, 2018,362:1400-1403. doi: 10.1126/science.aav0652
5. [5]
  Goodwin C A P, Ortu F, Reta D, Chilton N F, Mills D P. Molecular Magnetic Hysteresis at 60 Kelvin in Dysprosocenium[J]. Nature, 2017,548:439-442. doi: 10.1038/nature23447
6. [6]
  Alejandro C A, Yolimar G, Leonel L, Daniel A. High Performance Single-Molecule Magnets, Orbach or Raman Relaxation Suppression?[J]. InorgChem. Front., 2020,7:2478-2486.
7. [7]
  Chen Y C, Liu J L, Ungur L, Li Q W, Wang L F, Ni Z P, Chibotaru L F, Chen X P, Tong M L. Symmetry-Supported Magnetic Blocking at 20 K in Pentagonal Bipyramidal Dy(Ⅲ) Single-Ion Magnets[J]. J. Am. Chem. Soc., 2016,138(8):2829-2837. doi: 10.1021/jacs.5b13584
8. [8]
  Ungur L, Chibotaru L F. Magnetic Anisotropy in the Excited States of Low Symmetry Lanthanide Complexes[J]. Phys. Chem. Chem. Phys., 2011,13:20086-20090. doi: 10.1039/c1cp22689d
9. [9]
  Gould C A, Mcclain K R, Reta D, Kragskow J G C, Marchiori D A, Lachman E, Choi E S, Analytis J G, Britt R D, Chilton N F, Harvey B G, Long J R. Ultrahard Magnetism from Mixed-Valence Dilanthanide Complexes with Metal-Metal Bonding[J]. Science, 2022,375:198-202. doi: 10.1126/science.abl5470
10. [10]
  Jiang S D, Wang B W, Su G, Wang Z M, Gao S. A Mononuclear Dys- prosium Complex Featuring Single-Molecule Magnet Behavior[J]. Angew. Chem. Int. Ed., 2010,49:7448-7451. doi: 10.1002/anie.201004027
11. [11]
  Demir S, Gonzalez M I, Darago L E, Evans W J, Long J R. Giant Coercivity and High Magnetic Blocking Temperatures for N₂^3-Radical-Bridged Dilanthanide Complexes upon Ligand Dissociation[J]. Nat. Commun., 2017,82144. doi: 10.1038/s41467-017-01553-w
12. [12]
  Dolinar B S, Alexandropoulos D I, Vignesh K R, James T A, Dunbar K R. Lanthanide Triangles Supported by Radical Bridging Ligands[J]. J. Am. Chem. Soc., 2018,140(3):908-911. doi: 10.1021/jacs.7b12495
13. [13]
  Peng Y, Powell A K. What do 3d-4f Butterflies Tell Us?[J]. CoordChem. Rev., 2021,426214390.
14. [14]
  Yang J W, Tian Y M, Tao J, Chen P, Li H F, Zhang Y Q, Yan P F, Sun W B. Modulation of the Coordination Environment around the Magnetic Easy Axis Leads to Significant Magnetic Relaxations in a Series of 3d-4f Schiff Complexes[J]. Inorg. Chem., 2018,57:8065-8077. doi: 10.1021/acs.inorgchem.8b00056
15. [15]
  Wen H R, Hu J H, Yang K, Zhang J L, Liu S J, Liao J S, Liu C M. Family of Chiral Zn^Ⅱ-Ln^Ⅲ (Ln=Dy and Tb) Heterometallic Complexes Derived from the Amine-Phenol Ligand Showing Multifunctional Properties[J]. Inorg. Chem., 2020,59:2811-2824. doi: 10.1021/acs.inorgchem.9b03164
16. [16]
  Souvik M, Apran M, Sanjit K, Ashutosh G. The Role of 3d-4f Exchange Interaction in SMM Behavior and Magnetic Refrigeration of Carbonato Bridged Cu₂^Ⅱ Ln₂^Ⅲ (Ln=Dy, Tb, Gd) Complexes of an Unsymmetrical N₂O₄ Donor Ligand[J]. Dalton Trans., 2019,48:15170-15183. doi: 10.1039/C9DT02627D
17. [17]
  Vignesh K R, Langly S K, Murray K S, Rajarman G. Quenching the Quantum Tunneling of Magnetization in Heterometallic Octanuclear TM₄^ⅡDy₄^Ⅲ (TM=Co and Cr) Single-Molecular Magnets by Modification of the Bridging Ligands and Enhancing the Magnetic Exchange Coupling[J]. Chem. Eur. J., 2017,23:1654-1666. doi: 10.1002/chem.201604835
18. [18]
  Osa S, Kido T, Matsumoto N, Re N, Pochaba A, Mrozinski J. A Tetranuclear 3d-4f Single Molecule Magnet: [Cu^ⅡLTb^Ⅲ (hfac)₂]₂[J]. J. Am. Chem. Soc., 2004,126:420-421. doi: 10.1021/ja037365e
19. [19]
  Liu C M, Zhang D Q, Hao X, Zhu D B. Assembly of Chiral 3d-4f Wheel-like Cluster Complexes with Achiral Ligands: Single-Molecule Magnetic Behavior and Magnetocaloric Effect[J]. Inorg. Chem. Front., 2020,7:3340-3351. doi: 10.1039/D0QI00632G
20. [20]
  Wang Z X, Zhang X, Zhang Y Z, Li M X, Zhao H H, Andruh M, Dunbar K R. Single-Chain Magnetic Behavior in a Hetero-tri-spin Complex Mediated by Supramolecular Interactions with TCNQF^·-Radicals[J]. Angew. Chem. Int. Ed., 2014,53:11567-11270. doi: 10.1002/anie.201407628
21. [21]
  Vieru V, Pasatoiu T D, Ungur L, Suturina E, Madalan A M, Duhayon C, Sutter J P, Andruh M, ChibotaruL F. Synthesis, Crystal Struc-tures, Magnetic Properties, and Theoretical Investigation of a New Series of Ni^Ⅱ-Ln^Ⅲ-W^Ⅴ Heterotrimetallics: Understanding the SMM Behavior of Mixed Polynuclear Complexes[J]. Inorg. Chem., 2016,55:12158-12171. doi: 10.1021/acs.inorgchem.6b01669
22. [22]
  Huang X C, Zhou C, Wei H Y, Wang X Y. End-On Azido-Bridged 3d-4f Complexes Showing Single-Molecule Magnet Property[J]. Inorg. Chem., 2013,52:7314-7316. doi: 10.1021/ic400986y
23. [23]
  Huang X C, Vieru V, Chibotaru L F, Wernsdorfer W, Jiang S D, Wang X Y. Determination of Magnetic Anisotropy in a Multinuclear Tb^Ⅲ-Based Single-Molecule Magnet[J]. Chem. Commun., 2015,51:10373-10376. doi: 10.1039/C5CC03089G
24. [24]
  Bain G A, Berry J F. Diamagnetic Corrections and Pascal′s Con-stants[J]. J. Chem. Educ., 2008,85:532-536. doi: 10.1021/ed085p532
25. [25]
  SAINT, Version 7.68A, Bruler AXS, Inc., Madison, WI, 2008.
26. [26]
  Sheldrick G M. SHELXTL, Version 6.14, Bruker AXS, Inc., Madison, WI, 2000-2003.
27. [27]
  Sheldrick G M. Recent Upgrade to the SHELXL Refinement Program is also Available[J]. Acta Crystallogr. Sect. C, 2015.
28. [28]
  Lo W K, Wong W K, Wong W Y, Guo J P, Yeung K T, Cheng Y K, Yang X P, Jones R A. Heterobimetallic Zn(Ⅱ)-Ln(Ⅲ) Phenylene- Bridged Schiff Base Complexes, Computational Studies, and Evidence for Singlet Energy Transfer as the Main Pathway in the Sensitization of Near-Infrared Nd³⁺ Luminescence[J]. Inorg. Chem., 2006,45:9315-9325. doi: 10.1021/ic0610177
29. [29]
  Chuan H L, Jian H J, Ping Y, Li M T, Xu L, Sheng X X, Xiu P, Xu T, Jin Q X, Yi Z, Ming A X, Qiang G L. Preparation, Structure, and Thermochemical Properties of a Copper((Ⅱ)) Schiff-Base Complex[J]. J. Therm. Anal. Calorim., 2015,119:1285-1292. doi: 10.1007/s10973-014-4232-2
30. [30]
  Melby L R, Harder R J, Hertler W R, Mahler W, Benson R E, Mochel W E. Substituted Quinodimethans. Ⅱ. Anion-Radical Derivatives and Complexes of 7, 7, 8, 8-Tetracyanoquinodimethan[J]. J. Am. Chem. Soc., 1962,84:3374-3387.
31. [31]
  Llunell M, Casanova D, Cirera J, Alemany P, Alvarez S. SHAPE, Version 2.1, University of Barcelona, Spain, 2013.
32. [32]
  Ballesteros - Rivas M, Ota A, Reinheimer E, Prosvirin A, Valldes-Martinez J, Dunbar K R. Highly Conducting Coordination Polymers Based on Infinite M(4, 4'-bpy) Chains Flanked by Regular Stacks of Non-integer TCNQ Radicals[J]. Angew. Chem. Int. Ed., 2011,50:9703-9707. doi: 10.1002/anie.201101658
33. [33]
  Kahn O. Molecular Magnetism. New York: VCH, 1993.
34. [34]
  Costes J P, Dahan F, Dupuis A, Laurent J P. Nature of the Magnetic Interaction in the (Cu²⁺, Ln³⁺) Pairs: An Empirical Approach Based on the Comparison between Homologous (Cu²⁺, Ln³⁺) and (NiLS²⁺, Ln³⁺) Complexes[J]. Chem. Eur. J., 1998,4:1616-1620. doi: 10.1002/(SICI)1521-3765(19980904)4:9<1616::AID-CHEM1616>3.0.CO;2-A
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