Citation: Wan Rui-Chen, Wu Si-Guo, Liu Jun-Liang, Jia Jian-Hua, Huang Guo-Zhang, Li Quan-Wen, Tong Ming-Liang. Modulation of Slow Magnetic Relaxation for Tb(Ⅲ)-Metallacrown Complexes by Controlling Axial Halide Coordination[J]. Acta Chimica Sinica, ;2020, 78(5): 412-418. doi: 10.6023/A20030077 shu

Modulation of Slow Magnetic Relaxation for Tb(Ⅲ)-Metallacrown Complexes by Controlling Axial Halide Coordination

Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275

Corresponding author: Jia Jian-Hua, jiajh3@mail.sysu.edu.cn Tong Ming-Liang, tongml@mail.sysu.edu.cn
Received Date: 19 March 2020
Available Online: 20 April 2020
Fund Project: the National Natural Science Foundation of China 21620102002the Fundamental Research Funds for Central Universities 19lgyjs31the Science and Technology Plan of Guangzhou 201806010192the Natural Science Foundation of Guangdong Province 2017A030313059Project supported by the National Natural Science Foundation of China (Nos. 21771198, 21620102002), the Natural Science Foundation of Guangdong Province (No. 2017A030313059), the Science and Technology Plan of Guangzhou (No. 201806010192) and the Fundamental Research Funds for Central Universities (No. 19lgyjs31)the National Natural Science Foundation of China 21771198

Figures(8)

Single-molecule magnets (SMMs), exhibiting magnetic bistability and slow magnetization relaxation, have fascinated scientific community for their promising applications in data storage and information processing. Great development has been achieved in lanthanide-based SMMs due to the unquenched orbital momentum and strong anisotropy of lanthanide ions. According to the crystal-field theory, the magnetic anisotropy of lanthanide ions arises from crystal-field splitting. Appropriate arrangement of coordination environment of lanthanide ion (including the local symmetry as well as the charge distribution) is key to design high-performance SMMs. However, it still remains a huge challenge to generate lanthanide-containing compounds with certain coordination environment. Taking advantage of metallacrown (MC) approach, herein a series of 3d-4f complexes {TbNi₅X₂} (X=F, Cl, Br) were successfully isolated via solvothermal reactions. To obtain these complexes, a mixture of stoichiometric metal salt and quinaldichdroxamic acid with excess of pyridine derivative was dissolved in methanol and then heated at 75℃ for 2 d. X-ray single-crystal diffraction analysis indicated that the Tb(Ⅲ) site equatorially coordinates with[15-MC_Ni(Ⅱ)-5], whilst is axially capped by halide ions. As a result, the lanthanide ion possesses high axiality with a pentagonal bipyramid geometry (D_5h). Alternative current magnetic susceptibility data revealed that the electrostatic interactions between f-electrons and ligand electrons play an important role in modulating the magnetic relaxation dynamics. Maximizing the axial charge density in {TbNi₅F₂} where the[F-Ln-F]⁺ moiety is firstly reported in lanthanide chemistry, the oblate Tb(Ⅲ) is placed in a judicious crystal field. The out-of-phase signal of {TbNi₅F₂} shows obvious temperature and frequency dependence under 1 kOe applied dc field. Additionally, the slow magnetization relaxation of {TbNi₅F₂} can be fitted by the power law or Arrhenius plot with reversal barrier of 19.0 K. By lowering the electrostatic interactions of axial ligation, the out-of-phase signal significantly weakens in {TbNi₅Cl₂} and even vanishes in {TbNi₅Br₂}. The decline of magnetic anisotropy in {TbNi₅Cl₂} and {TbNi₅Br₂} accelerates the fast quantum tunneling of magnetization. The results demonstrate for the first time that the Off/Part/On slow magnetization relaxation can be modulated via the improvement of electronegativity of axial ligands.
- lanthanide,
- Tb (Ⅲ) ion,
- metallacrown,
- slow magnetic relaxation,
- single-molecule magnets
1. [1]
  Sessoli, R.; Gatteschi, D.; Caneschi, A.; Novak, M. A. Nature 1993, 365, 141. doi: 10.1038/365141a0
2. [2]
  Gatteschi, D.; Sessoli, R.; Villain, J. Molecular Nanomagnets, Oxford University Press, Oxford, 2006.
3. [3]
  Meng, Y.-S.; Jiang, S.-D.; Wang, B.-W.; Gao, S. Acc. Chem. Res. 2016, 49, 2381. doi: 10.1021/acs.accounts.6b00222
4. [4]
  Ungur, L.; Lin, S.-Y.; Tang, J.; Chibotaru, L. F. Chem. Soc. Rev. 2014, 43, 6894. doi: 10.1039/C4CS00095A
5. [5]
  McClain, K. R.; Gould, C. A.; Chakarawet, K.; Teat, S. J.; Groshens, T. J.; Long, J. R.; Harvey, B. G. Chem. Sci. 2018, 9, 8492. doi: 10.1039/C8SC03907K
6. [6]
  Gould, C. A.; McClain, K. R.; Yu, J. M.; Groshens, T. J.; Furche, F.; Harvey, B. G.; Long, J. R. J. Am. Chem. Soc. 2019, 141, 12967. doi: 10.1021/jacs.9b05816
7. [7]
  Goodwin, C. A.; Ortu, F.; Reta, D.; Chilton, N. F.; Mills, D. P. Nature 2017, 548, 439. doi: 10.1038/nature23447
8. [8]
  Guo, F. S.; Day, B. M.; Chen, Y. C.; Tong, M. L.; Mansikkamaki, A.; Layfield, R. A. Angew. Chem., Int. Ed. 2017, 56, 11445. doi: 10.1002/anie.201705426
9. [9]
  Guo, F.-S.; Day, B. M.; Chen, Y.-C.; Tong, M.-L.; Mansikkamaki, A.; Layfield, R. A. Science 2018, 362, 1400. doi: 10.1126/science.aav0652
10. [10]
  Guo, P.-H.; Liao, X.-F.; Leng, J.-D.; Tong, M.-L. Acta Chim. Sinica 2013, 71, 173.
11. [11]
  Tian, H.-Q.; Zheng, L.-M. Acta Chim. Sinica 2020, 78, 34.
12. [12]
  Velkos, G.; Krylov, D. S.; Kirkpatrick, K.; Spree, L.; Dubrovin, V.; Bgchner, B.; Avdoshenko, S. M.; Bezmelnitsyn, V.; Davis, S.; Faust, P.; Duchamp, J.; Dorn, H. C.; Popov, A. A. Angew. Chem., Int. Ed. 2019, 58, 5891. doi: 10.1002/anie.201900943
13. [13]
  Li, H.; Meng, X.; Wang, M.; Wang, Y.-X.; Shi, W.; Cheng, P. Chin. J. Chem. 2019, 37, 373. doi: 10.1002/cjoc.201800589
14. [14]
  Gou, X.-S.; Wang, M.-M.; Meng, Q.-Q.; Cheng, P. Chin. J. Inorg. Chem. 2019, 35, 2013. doi: 10.11862/CJIC.2019.232
15. [15]
  Yan, H.; Li, Q.-W.; Liu, J.-L.; Jia, J.-H.; Tong, M.-L. J. Chin. Soc. Rare Earths 2016, 34, 726.
16. [16]
  Liu, K.; Zhang, X.; Meng, X.; Shi, W.; Cheng, P.; Powell, A. K. Chem. Soc. Rev. 2016, 45, 2423. doi: 10.1039/C5CS00770D
17. [17]
  (a) Sievers, J. Z. Phys. B: Condens. Matter 1982, 45, 289. (b) Rinehart, J. D.; Long, J. R. Chem. Sci. 2011, 2, 2078.
18. [18]
  Liu, J.-L.; Chen, Y.-C.; Zheng, Y.-Z.; Lin, W.-Q.; Ungur, L.; Wernsdorfer, W.; Chibotaru, L. F.; Tong, M.-L. Chem. Sci. 2013, 4, 3310. doi: 10.1039/c3sc50843a
19. [19]
  Liu, J.-L.; Chen, Y.-C.; Tong, M.-L. Chem. Soc. Rev. 2018, 47, 2431. doi: 10.1039/C7CS00266A
20. [20]
  Liu, J.-L.; Wu, J.-Y.; Chen, Y.-C.; Mereacre, V.; Powell, A. K.; Ungur, L.; Chibotaru, L. F.; Chen, X.-M.; Tong, M.-L. Angew. Chem., Int. Ed. 2014, 53, 12966. doi: 10.1002/anie.201407799
21. [21]
  Huang, G.-Z.; Ruan, Z.-Y.; Zheng, J.-Y.; Chen, Y.-C.; Wu, S.-G.; Liu, J.-L.; Tong, M.-L. Sci. China, Chem. 2020, 63, DOI:10.1007/s11426-020-9746-x. doi: 10.1007/s11426-020-9746-x
22. [22]
  Huang, G.-Z.; Ruan, Z. Y.; Zheng, J. Y.; Wu, J. Y.; Chen, Y. C.; Li, Q. W.; Akhtar, M. N.; Liu, J. L.; Tong, M. L. Sci. China, Chem. 2018, 61, 1399. doi: 10.1007/s11426-018-9310-y
23. [23]
  Liu, J.; Chen, Y. C.; Liu, J. L.; Vieru, V.; Ungur, L.; Jia, J. H.; Chibotaru, L. F.; Lan, Y. H.; Wernsdorfer, W.; Gao, S.; Chen, X. M.; Tong, M. L. J. Am. Chem. Soc. 2016, 138, 5441. doi: 10.1021/jacs.6b02638
24. [24]
  Chen, Y. C.; Liu, J. L.; Ungur, L.; Liu, J.; Li, Q. W.; Wang, L. F.; Ni, Z. P.; Chibotaru, L. F.; Chen, X. M.; Tong, M. L. J. Am. Chem. Soc. 2016, 138, 2829. doi: 10.1021/jacs.5b13584
25. [25]
  Chen, Y.-C.; Liu, J.-L.; Wernsdorfer, W.; Liu, D.; Chibotaru, L. F.; Chen, X. M.; Tong, M. L. Angew. Chem., Int. Ed. 2017, 56, 4996. doi: 10.1002/anie.201701480
26. [26]
  Mezei, G.; Zaleski, C. M.; Pecoraro, V. L. Chem. Rev. 2007, 107, 4933. doi: 10.1021/cr078200h
27. [27]
  Happ, P.; Plenk, C.; Rentschler, E. Coord. Chem. Rev. 2015, 289, 238.
28. [28]
  Li, Q.-W.; Liu, J.-L.; Jia, J.-H.; Chen, Y.-C.; Liu, J.; Wang, L.-F.; Tong, M.-L. Chem. Commun. 2015, 51, 10291. doi: 10.1039/C5CC03389F
29. [29]
  Li, Q.-W.; Wan, R.-C.; Chen, Y.-C.; Liu, J.-L.; Wang, L.-F.; Jia, J.-H.; Chilton, N. F.; Tong, M.-L. Chem. Commun. 2016, 52, 13365. doi: 10.1039/C6CC06924J
30. [30]
  Carlin, R. L. Translated by Wan, C. D. Magnetochemistry, Nanjing University Press, Nanjing, 1990.
31. [31]
  Wang, J.; Ruan, Z.-Y.; Li, Q.-W.; Chen, Y.-C.; Huang, G.-Z.; Liu, J.-L.; Reta, D.; Chilton, N. F.; Wang, Z.-X.; Tong, M.-L. Dalton Trans. 2019, 48, 1686. doi: 10.1039/C8DT04814B
32. [32]
  Cole, K. S.; Cole, R. H. J. Chem. Phys. 1941, 9, 341. doi: 10.1063/1.1750906
33. [33]
  Liu, J.-L.; Yuan, K.; Leng, J.-D.; Ungur, L.; Wernsdorfer, W.; Guo, F.-S.; Chibotaru, L. F.; Tong, M.-L. Inorg. Chem. 2012, 51, 8538. doi: 10.1021/ic301115b
34. [34]
  Bruker, SAINT, Version V8. 37A, Madison, 2015.
35. [35]
  Bruker, SADABS, Version 2014/5, Madison, 2014.
36. [36]
  Bruker, SHELXTL, Software Version 6. 12, Madison, 2001.
37. [37]
  Sheldrick, G. M. Acta Cryst. 2008, A64, 112.
38. [38]
  Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. J. Appl. Crystallogr. 2009, 42, 339. doi: 10.1107/S0021889808042726
39. [39]
  Spek, A. L. Acta Cryst. 2015, C71, 9.
1. [1]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
2. [2]
  Hongdao LI , Shengjian ZHANG , Hongmei DONG . Magnetic relaxation and luminescent behavior in nitronyl nitroxide-based annuluses of rare-earth ions. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 972-978. doi: 10.11862/CJIC.20230411
3. [3]
  Rui Li , Huan Liu , Yinan Jiao , Shengjian Qin , Jie Meng , Jiayu Song , Rongrong Yan , Hang Su , Hengbin Chen , Zixuan Shang , Jinjin Zhao . 卤化物钙钛矿的单双向离子迁移. Acta Physico-Chimica Sinica, 2024, 40(11): 2311011-. doi: 10.3866/PKU.WHXB202311011
4. [4]
  Liang TANG , Jingfei NI , Kang XIAO , Xiangmei LIU . Synthesis and X-ray imaging application of lanthanide-organic complex-based scintillators. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1892-1902. doi: 10.11862/CJIC.20240139
5. [5]
  Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu . d带中心调控过渡金属单原子负载COF吸附O₂的理论计算研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2407013-. doi: 10.3866/PKU.WHXB202407013
6. [6]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
7. [7]
  Yingran Liang , Fei Wang , Jiabao Sun , Hongtao Zheng , Zhenli Zhu . Construction and Application of a New Experimental Device for Determination of Alkaline Metal Elements by Plasma Atomic Emission Spectrometry Based on Solution Cathode Glow Discharge: An Alternative Approach for Fundamental Teaching Experiments in Emission Spectroscopy. University Chemistry, 2024, 39(5): 380-387. doi: 10.3866/PKU.DXHX202312024
8. [8]
  Pingwei Wu . Application of Diamond Software in Simplex Teaching. University Chemistry, 2024, 39(3): 118-121. doi: 10.3866/PKU.DXHX202311043
9. [9]
  Wenjun Zheng . Application in Inorganic Synthesis of Ionic Liquids. University Chemistry, 2024, 39(8): 163-168. doi: 10.3866/PKU.DXHX202401020
10. [10]
  Zitong Chen , Zipei Su , Jiangfeng Qian . Aromatic Alkali Metal Reagents: Structures, Properties and Applications. University Chemistry, 2024, 39(8): 149-162. doi: 10.3866/PKU.DXHX202311054
11. [11]
  Hong LI , Xiaoying DING , Cihang LIU , Jinghan ZHANG , Yanying RAO . Detection of iron and copper ions based on gold nanorod etching colorimetry. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 953-962. doi: 10.11862/CJIC.20230370
12. [12]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
13. [13]
  Doudou Qin , Junyang Ding , Chu Liang , Qian Liu , Ligang Feng , Yang Luo , Guangzhi Hu , Jun Luo , Xijun Liu . Addressing Challenges and Enhancing Performance of Manganese-based Cathode Materials in Aqueous Zinc-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(10): 2310034-. doi: 10.3866/PKU.WHXB202310034
14. [14]
  Feiya Cao , Qixin Wang , Pu Li , Zhirong Xing , Ziyu Song , Heng Zhang , Zhibin Zhou , Wenfang Feng . Magnesium-Ion Conducting Electrolyte Based on Grignard Reaction: Synthesis and Properties. University Chemistry, 2024, 39(3): 359-368. doi: 10.3866/PKU.DXHX202308094
15. [15]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065
16. [16]
  Dongqi Cai , Fuping Tian , Zerui Zhao , Yanjuan Zhang , Yue Dai , Feifei Huang , Yu Wang . Exploration of Factors Influencing the Determination of Ion Migration Number by Hittorf Method. University Chemistry, 2024, 39(4): 94-99. doi: 10.3866/PKU.DXHX202310031
17. [17]
  Jiayu Tang , Jichuan Pang , Shaohua Xiao , Xinhua Xu , Meifen Wu . Improvement for Measuring Transference Numbers of Ions by Moving-Boundary Method. University Chemistry, 2024, 39(5): 193-200. doi: 10.3866/PKU.DXHX202311021
18. [18]
  Yifeng Xu , Jiquan Liu , Bin Cui , Yan Li , Gang Xie , Ying Yang . “Xiao Li’s School Adventures: The Working Principles and Safety Risks of Lithium-ion Batteries”. University Chemistry, 2024, 39(9): 259-265. doi: 10.12461/PKU.DXHX202404009
19. [19]
  Chunmei GUO , Weihan YIN , Jingyi SHI , Jianhang ZHAO , Ying CHEN , Quli FAN . Facile construction and peroxidase-like activity of single-atom platinum nanozyme. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1633-1639. doi: 10.11862/CJIC.20240162
20. [20]
  Zuozhong Liang , Lingling Wei , Yiwen Cao , Yunhan Wei , Haimei Shi , Haoquan Zheng , Shengli Gao . Exploring the Development of Undergraduate Scientific Research Ability in Basic Course Instruction: A Case Study of Alkali and Alkaline Earth Metal Complexes in Inorganic Chemistry. University Chemistry, 2024, 39(7): 247-263. doi: 10.3866/PKU.DXHX202310103

Get Citation

PDF

XML

Metrics

PDF Downloads(18)
Abstract views(1952)
HTML views(290)

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