Citation: Lingling Su, Qunyan Wu, Congzhi Wang, Jianhui Lan, Weiqun Shi. Theoretical design of polyazole based ligands for the separation of Am(Ⅲ)/Eu(Ⅲ)[J]. Chinese Chemical Letters, ;2024, 35(8): 109402. doi: 10.1016/j.cclet.2023.109402 shu

Theoretical design of polyazole based ligands for the separation of Am(Ⅲ)/Eu(Ⅲ)

Lingling Su ^{a, b} ,
Qunyan Wu ^{b, *,} ,
Congzhi Wang ^b ,
Jianhui Lan ^b ,
Weiqun Shi ^{b, *,}

a.
School of Nuclear Science and Technology, University of South China, Hengyang 421001, China
b.
Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

wuqy@ihep.ac.cn

shiwq@ihep.ac.cn

Received Date: 30 August 2023
Revised Date: 4 December 2023
Accepted Date: 11 December 2023
Available Online: 21 December 2023

Figures(9)

The extraction of radioactive minor actinides (An(Ⅲ)) from lanthanides (Ln(Ⅲ)) is an extremely important step in nuclear waste reprocessing. Designing ligands with high-performance actinide-selectivity remains an essential task. Recent works have reported that some polyazole based ligands exhibit good An(Ⅲ)/Ln(Ⅲ) separation performance. Herein, we first evaluated the effects of different polyazole side chains on the Am(Ⅲ)/Eu(Ⅲ) selectivity by exploring three pyridine-derived polyazole ligands L¹, L² and L³ with 1,2,4-triazole, 1,2,3-triazole, and pyrazole side chains, respectively, using scalar relativistic theoretical methods. The coordination structures, bonding properties and thermodynamic behaviors of AmL(NO₃)₃ and EuL(NO₃)₃ complexes were investigated, which clarifies that the side chains do affect the electronic structure of ligand and its selectivity for Am(Ⅲ)/Eu(Ⅲ) ions. Moreover, L¹ with 1,2,4-triazole side chains exhibited the highest selectivity for Am(Ⅲ) over Eu(Ⅲ) while the lowest complexation ability for metal ions among the three pyridine-derived polyazole ligands. Subsequently, we designed a new ligand L⁴ containing 1,2,4-triazole side chains and a preorganized phenanthroline backbone. Theoretically, such a new ligand was verified to show stronger complexation ability and higher selectivity for Am(Ⅲ)/Eu(Ⅲ) ions than L¹. This work clarifies the complexation nature of polyazole based ligands with Am(Ⅲ)/Eu(Ⅲ) ions and provides design strategies for highly efficient polyazole based ligands for An(Ⅲ)/Ln(Ⅲ) separation.
- Solvent extraction,
- Am(Ⅲ)/Eu(Ⅲ) separation,
- Polyazole based ligands,
- Design strategy,
- Density functional theory
1. [1]
  R.C. Ewing, Nat. Mater. 14 (2015) 252–257. doi: 10.1038/nmat4226
2. [2]
  J. Veliscek-Carolan, J. Hazard. 318 (2016) 266–281. doi: 10.1016/j.jhazmat.2016.07.027
3. [3]
  M. Salvatores, G. Palmiotti, Prog. Part. Nucl. Phys. 66 (2011) 144–166. doi: 10.1016/j.ppnp.2010.10.001
4. [4]
  A. Salvatores, Nucl. Eng. Des. 235 (2005) 805–816. doi: 10.1016/j.nucengdes.2004.10.009
5. [5]
  J.N. Mathur, M.S. Murali, K.L. Nash, Solvent Extr. Ion. Exch. 19 (2001) 357–390. doi: 10.1081/SEI-100103276
6. [6]
  K.L. Nash, Handbook on the Physics and Chemistry of Rare Earths, Elsevier, 1994, pp. 197–238.
7. [7]
  A. Khayambashi, L. Chen, X. Dong, et al., Chin. Chem. Lett. 33 (2022) 3429–3434. doi: 10.1016/j.cclet.2022.02.011
8. [8]
  L. Xu, N. Pu, G. Y, et al., Inorg. Chem. Front. 7 (2020) 1726–1740. doi: 10.1039/d0qi00200c
9. [9]
  X. Yang, S.H. Wang, L. Xu, et al., Inorg. Chem. Front. 9 (2022) 4671–4684. doi: 10.1039/d2qi01153k
10. [10]
  T.Y. Xiu, S.M. Zhang, P. Ren, et al., Chin. Chem. Lett. 34 (2023) 108440. doi: 10.1016/j.cclet.2023.108440
11. [11]
  D.S. Tian, Y.Y. Liu, Y. Kang, et al., ACS Cent. Sci. 9 (2023) 1642–1649. doi: 10.1021/acscentsci.3c00504
12. [12]
  R.G. Pearson, J. Am. Chem. Soc. 85 (1963) 3533–3539. doi: 10.1021/ja00905a001
13. [13]
  A. Leoncini, J. Huskens, W. Verboom, Chem. Soc. Rev. 46 (2017) 7229–7273. doi: 10.1039/C7CS00574A
14. [14]
  Z.R. Ye, Q.Y. Wu, C.Z. Wang, et al., Inorg. Chem. 60 (2021) 16409–16419. doi: 10.1021/acs.inorgchem.1c02256
15. [15]
  A. Geist, P.J. Panak, Solvent Extr. Ion. Exch. 39 (2021) 128–151. doi: 10.1080/07366299.2020.1831235
16. [16]
  C. Madic, M.J. Hudson, Report EUR 18038EN. Nuclear Science and Technology, 1998.
17. [17]
  Z. Kolarik, U. Müllich, F. Gassner, Solvent Extr. Ion. Exch. 17 (1999) 23–32. doi: 10.1080/07360299908934598
18. [18]
  F.W. Lewis, L.M. Harwood, M.J. Hudson, et al., J. Am. Chem. Soc. 133 (2011) 13093–13102. doi: 10.1021/ja203378m
19. [19]
  M.G.B. Drew, M.J. Hudson, P.B. Iveson, et al., Dalton Trans. (1999) 2433–2440.
20. [20]
  A. Bremer, C.M. Ruff, D. Girnt, et al., Inorg. Chem. 51 (2012) 5199–5207. doi: 10.1021/ic3000526
21. [21]
  D.P. Su, Y. Liu, S.M. Li, et al., Eur. J. Inorg. Chem. (2017) 651–658 2017.
22. [22]
  Y. Liu, X.Y. Yang, S.D. Ding, et al., Inorg. Chem. 57 (2018) 5782–5790. doi: 10.1021/acs.inorgchem.8b00074
23. [23]
  J.R. Wang, D.P. Su, D.Q. Wang, et al., Inorg. Chem. 54 (2015) 10648–10655. doi: 10.1021/acs.inorgchem.5b01452
24. [24]
  X.H. Kong, Q.Y. Wu, C.Z. Wang, et al., J. Phys. Chem. A 122 (2018) 4499–4507. doi: 10.1021/acs.jpca.8b00177
25. [25]
  C. Kiefer, A.T. Wagner, B.B. Beele, et al., Inorg. Chem. 54 (2015) 7301–7308. doi: 10.1021/acs.inorgchem.5b00803
26. [26]
  E. Macerata, E. Mossini, S. Scaravaggi, et al., J. Am. Chem. Soc. 138 (2016) 7232–7235. doi: 10.1021/jacs.6b03106
27. [27]
  A.C. Edwards, P. Mocilac, A. Geist, et al., Chem. Commun. 53 (2017) 5001–5004. doi: 10.1039/C7CC01855J
28. [28]
  A. Ossola, E. Macerata, E. Mossini, et al., J. Radioanal. Nucl. Ch. 318 (2018) 2013–2022. doi: 10.1007/s10967-018-6253-y
29. [29]
  P. Weßling, M. Maag, G. Baruth, et al., Inorg. Chem. 61 (2022) 17719–17729. doi: 10.1021/acs.inorgchem.2c02871
30. [30]
  F. Galluccio, E. Macerata, P. Weßling, et al., Inorg. Chem. 61 (2022) 18400–18411. doi: 10.1021/acs.inorgchem.2c02332
31. [31]
  L.K. Liu, S.B. Xie, H.B. Lv, et al., Chin. Chem. Lett. 33 (2022) 3439–3443. doi: 10.1016/j.cclet.2022.04.001
32. [32]
  Y.A. Ustynyuk, M.Y. Alyapyshev, V.A. Babain, et al., Russ. Chem. Rev. 85 (2016) 917–942. doi: 10.1070/RCR4588
33. [33]
  X. Zhang, S.L. Adelman, B.T. Arko, et al., Inorg. Chem. 61 (2022) 11556–11570. doi: 10.1021/acs.inorgchem.2c00534
34. [34]
  C. Ebenezer, R. Vijay Solomon, Inorg. Chem. Front. 8 (2021) 3012–3024. doi: 10.1039/d1qi00097g
35. [35]
  R.C. Chapleski Jr., A.S. Ivanov, K.A. Peterson, et al., Phys. Chem. Chem. Phys. 23 (2021) 19558–19570. doi: 10.1039/d1cp02466c
36. [36]
  J.P. Yu, K. Liu, Q.Y. Wu, et al., Chinese J. Chem. 39 (2021) 2125–2131. doi: 10.1002/cjoc.202100149
37. [37]
  G.J.P. Deblonde, M.P. Kelley, J. Su, et al., Angew. Chem. Int. Ed. 57 (2018) 4521–4526. doi: 10.1002/anie.201709183
38. [38]
  J.N. Cross, J. Su, E.R. Batista, et al., J. Am. Chem. Soc. 139 (2017) 8667–8677. doi: 10.1021/jacs.7b03755
39. [39]
  J. Su, E.R. Batista, K.S. Boland, et al., J. Am. Chem. Soc. 140 (2018) 17977–17984. doi: 10.1021/jacs.8b09436
40. [40]
  Q.Y. Wu, Y.T. Song, L. Ji, et al., Phys. Chem. Chem. Phys. 19 (2017) 26969–26979. doi: 10.1039/C7CP04625A
41. [41]
  C. Wang, Q.Y. Wu, X.H. Kong, et al., Inorg. Chem. 58 (2019) 10047–10056. doi: 10.1021/acs.inorgchem.9b01200
42. [42]
  X.H. Kong, Q.Y. Wu, J.H. Lan, et al., Inorg. Chem. 57 (2018) 14810–14820. doi: 10.1021/acs.inorgchem.8b02550
43. [43]
  X.P. Lei, Q.Y. Wu, C.Z. Wang, et al., Dalton Trans. 51 (2022) 16659–16667. doi: 10.1039/d2dt02474h
44. [44]
  X.P. Lei, Q.Y. Wu, C.Z. Wang, et al., Inorg. Chem. 62 (2023) 2705–2714. doi: 10.1021/acs.inorgchem.2c03823
45. [45]
  Y.M. Chen, C.Z. Wang, Q.Y. Wu, et al., Inorg. Chem. 59 (2020) 3221–3231. doi: 10.1021/acs.inorgchem.9b03604
46. [46]
  Z.R. Ye, Q.Y. Wu, C.Z. Wang, et al., Inorg. Chem. 61 (2022) 6110–6119. doi: 10.1021/acs.inorgchem.2c00232
47. [47]
  Y. Zou, J.H. Lan, L.Y. Yuan, et al., Inorg. Chem. 62 (2023) 4581–4589. doi: 10.1021/acs.inorgchem.2c04476
48. [48]
  Y. Zou, J.H. Lan, L.Y. Yuan, et al., Inorg. Chem. 61 (2022) 15423–15431. doi: 10.1021/acs.inorgchem.2c01952
49. [49]
  A. Bhattacharyya, T. Gadly, A.S. Kanekar, et al., Inorg. Chem. 57 (2018) 5096–5107. doi: 10.1021/acs.inorgchem.8b00142
50. [50]
  C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785–789. doi: 10.1103/PhysRevB.37.785
51. [51]
  M.J. Frisch, G.W. Trucks, H.B. Schlegel, et al., Gaussian 16, Revision B, Gaussian, Inc., Wallingford, CT, 2016.
52. [52]
  M. Dolg, H. Stoll, H. Preuss, J. Chem. Phys. 90 (1989) 1730–1734. doi: 10.1063/1.456066
53. [53]
  W. Küchle, M. Dolg, H. Stoll, J. Chem. Phys. 100 (1994) 7535–7542. doi: 10.1063/1.466847
54. [54]
  X.Y. Cao, M. Dolg, J. Mol. Struct. 581 (2002) 139–147. doi: 10.1016/S0166-1280(01)00751-5
55. [55]
  X.Y. Cao, M. Dolg, H. Stoll, J. Chem. Phys. 118 (2002) 487–496.
56. [56]
  X.Y. Cao, M. Dolg, J. Mol. Struct. 673 (2004) 203–209. doi: 10.1016/j.theochem.2003.12.015
57. [57]
  G.A. Shamov, G. Schreckenbach, R.L. Martin, et al., Inorg. Chem. 47 (2008) 1465–1475. doi: 10.1021/ic7015403
58. [58]
  G.A. Shamov, G. Schreckenbach, J. Phys. Chem. A 109 (2005) 10961–10974. doi: 10.1021/jp053522f
59. [59]
  J. Narbutt, A. Wodyński, M. Pecul, Dalton Trans. 44 (2015) 2657–2666. doi: 10.1039/C4DT02657H
60. [60]
  A. Zaiter, B. Amine, Y. Bouzidi, et al., Inorg. Chem. 53 (2014) 4687–4697. doi: 10.1021/ic500361b
61. [61]
  C. Clavaguéra-Sarrio, V. Vallet, D. Maynau, et al., J. Chem. Phys. 121 (2004) 5312–5321. doi: 10.1063/1.1784412
62. [62]
  M. Cossi, N. Rega, G. Scalmani, et al., J. Comput. Chem. 24 (2003) 669–681. doi: 10.1002/jcc.10189
63. [63]
  V. Barone, M. Cossi, J. Phys. Chem. A 102 (1998) 1995–2001. doi: 10.1021/jp9716997
64. [64]
  J. Ho, A. Klamt, M.L. Coote, J. Phys. Chem. A 114 (2010) 13442–13444. doi: 10.1021/jp107136j
65. [65]
  T. Lu, F. Chen, J. Comput. Chem. 33 (2012) 580–592. doi: 10.1002/jcc.22885
66. [66]
  I. Mayer, Chem. Phys. Lett. 97 (1983) 270–274. doi: 10.1016/0009-2614(83)80005-0
67. [67]
  A.E. Reed, F. Weinhold, J. Chem. Phys. 78 (1983) 4066–4073. doi: 10.1063/1.445134
68. [68]
  A.E. Reed, R.B. Weinstock, F. Weinhold, J. Chem. Phys. 83 (1985) 735–746. doi: 10.1063/1.449486
69. [69]
  R.F.W. Bader, C.F. Matta, Inorg. Chem. 40 (2001) 5603–5611. doi: 10.1021/ic010165o
70. [70]
  E. Espinosa, I. Alkorta, J. Elguero, et al., J. Chem. Phys. 117 (2002) 5529–5542. doi: 10.1063/1.1501133
71. [71]
  T. Ziegler, A. Rauk, Theor. Chem. Acc. 46 (1977) 1–10. doi: 10.1007/BF02401406
72. [72]
  G. te Velde, F.M. Bickelhaupt, E.J. Baerends, et al., J. Comput. Chem. 22 (2001) 931–967. doi: 10.1002/jcc.1056
73. [73]
  C. Fonseca Guerra, J.G. Snijders, G. te Velde, et al., Theor. Chem. Acc. 99 (1998) 391–403.
74. [74]
  T.Z.E.J. Baerends, J. Autschbach, D. Bashford, et al., ADF2022, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands, URL: http://www.scm.com.
75. [75]
  R.G. Parr, R.G. Pearson, J. Am. Chem. Soc. 105 (1983) 7512–7516. doi: 10.1021/ja00364a005
76. [76]
  R. Shannon, Acta Crystallogr. A 32 (1976) 751–767. doi: 10.1107/S0567739476001551
77. [77]
  M.P. Jensen, A.H. Bond, J. Am. Chem. Soc. 124 (2002) 9870–9877. doi: 10.1021/ja0178620
78. [78]
  D. Cremer, E. Kraka, J. Am. Chem. Soc. 107 (1985) 3811–3819. doi: 10.1021/ja00299a010
79. [79]
  W.H. Tu, S.J. Zeng, Y. Bai, et al., Ind. Chem. Mater. 1 (2023) 262–270. doi: 10.1039/d2im00041e
80. [80]
  P. Thakur, J.L. Conca, G.R. Choppin, J. Solution Chem. 41 (2012) 599–615. doi: 10.1007/s10953-012-9826-3
1. [1]
  Xu Huang , Kai-Yin Wu , Chao Su , Lei Yang , Bei-Bei Xiao . Metal-organic framework Cu-BTC for overall water splitting: A density functional theory study. Chinese Chemical Letters, 2025, 36(4): 109720-. doi: 10.1016/j.cclet.2024.109720
2. [2]
  Yuxiang Zhang , Jia Zhao , Sen Lin . Nitrogen doping retrofits the coordination environment of copper single-atom catalysts for deep CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100415-100415. doi: 10.1016/j.cjsc.2024.100415
3. [3]
  Wei Chen , Pieter Cnudde . A minireview to ketene chemistry in zeolite catalysis. Chinese Journal of Structural Chemistry, 2024, 43(11): 100412-100412. doi: 10.1016/j.cjsc.2024.100412
4. [4]
  Jiajun Wang , Guolin Yi , Shengling Guo , Jianing Wang , Shujuan Li , Ke Xu , Weiyi Wang , Shulai Lei . Computational design of bimetallic TM₂@g-C₉N₄ electrocatalysts for enhanced CO reduction toward C₂ products. Chinese Chemical Letters, 2024, 35(7): 109050-. doi: 10.1016/j.cclet.2023.109050
5. [5]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
6. [6]
  Yu-Hang Li , Shuai Gao , Lu Zhang , Hanchun Chen , Chong-Chen Wang , Haodong Ji . Insights on selective Pb adsorption via O 2p orbit in UiO-66 containing rich-zirconium vacancies. Chinese Chemical Letters, 2024, 35(8): 109894-. doi: 10.1016/j.cclet.2024.109894
7. [7]
  Xin-Tong Zhao , Jin-Zhi Guo , Wen-Liang Li , Jing-Ping Zhang , Xing-Long Wu . Two-dimensional conjugated coordination polymer monolayer as anode material for lithium-ion batteries: A DFT study. Chinese Chemical Letters, 2024, 35(6): 108715-. doi: 10.1016/j.cclet.2023.108715
8. [8]
  Fanjun Kong , Yixin Ge , Shi Tao , Zhengqiu Yuan , Chen Lu , Zhida Han , Lianghao Yu , Bin Qian . Engineering and understanding SnS_0.5Se_0.5@N/S/Se triple-doped carbon nanofibers for enhanced sodium-ion batteries. Chinese Chemical Letters, 2024, 35(4): 108552-. doi: 10.1016/j.cclet.2023.108552
9. [9]
  Weiping Xiao , Yuhang Chen , Qin Zhao , Danil Bukhvalov , Caiqin Wang , Xiaofei Yang . Constructing the synergistic active sites of nickel bicarbonate supported Pt hierarchical nanostructure for efficient hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(12): 110176-. doi: 10.1016/j.cclet.2024.110176
10. [10]
  Ze Zhang , Lei Yang , Jin-Ru Liu , Hao Hu , Jian-Li Mi , Chao Su , Bei-Bei Xiao , Zhi-Min Ao . Improved oxygen electrocatalysis at FeN₄ and CoN₄ sites via construction of axial coordination. Chinese Chemical Letters, 2025, 36(2): 110013-. doi: 10.1016/j.cclet.2024.110013
11. [11]
  Chaozheng He , Menghui Xi , Chenxu Zhao , Ran Wang , Ling Fu , Jinrong Huo . Highly N₂ dissociation catalyst: Ir(100) and Ir(110) surfaces. Chinese Chemical Letters, 2025, 36(3): 109671-. doi: 10.1016/j.cclet.2024.109671
12. [12]
  Mianfeng Li , Haozhi Wang , Zijun Yang , Zexiang Yin , Yuan Liu , Yingmei Bian , Yang Wang , Xuerong Zheng , Yida Deng . Synergistic enhancement of alkaline hydrogen evolution reaction by role of Ni-Fe LDH introducing frustrated Lewis pairs via vacancy-engineered. Chinese Chemical Letters, 2025, 36(3): 110199-. doi: 10.1016/j.cclet.2024.110199
13. [13]
  Teng Wang , Jiachun Cao , Juan Li , Didi Li , Zhimin Ao . A novel photocatalytic mechanism of volatile organic compounds degradation on BaTiO₃ under visible light: Photo-electrons transfer from photocatalyst to pollutant. Chinese Chemical Letters, 2025, 36(3): 110078-. doi: 10.1016/j.cclet.2024.110078
14. [14]
  Dongdong YANG , Jianhua XUE , Yuanyu YANG , Meixia WU , Yujia BAI , Zongxuan WANG , Qi MA . Design and synthesis of two coordination polymers for the rapid detection of ciprofloxacin based on triphenylpolycarboxylic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2466-2474. doi: 10.11862/CJIC.20240266
15. [15]
  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
16. [16]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
17. [17]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
18. [18]
  Jun-Ting Mo , Zheng Wang . Achieving tunable long persistent luminescence in metal organic halides based on pyridine solvent. Chinese Chemical Letters, 2024, 35(9): 109360-. doi: 10.1016/j.cclet.2023.109360
19. [19]
  Meiling Xu , Xinyang Li , Pengyuan Liu , Junjun Liu , Xiao Han , Guodong Chai , Shuangling Zhong , Bai Yang , Liying Cui . A novel and visible ratiometric fluorescence determination of carbaryl based on red emissive carbon dots by a solvent-free method. Chinese Chemical Letters, 2025, 36(2): 109860-. doi: 10.1016/j.cclet.2024.109860
20. [20]
  Qiang Wu , Baofeng Wang . Exploring synthetic strategy for stabilizing nickel-rich layered oxide cathodes through structural design. Chinese Chemical Letters, 2024, 35(12): 110089-. doi: 10.1016/j.cclet.2024.110089

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(562)
HTML views(4)

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