Citation: Liying Wang, Jiajia Li, Xin Liu, Qianqian Liu, Jiaxin Li, Song Liang, Hong-Ying Zang. Ligand-directed assembly of [Mo₂O₂S₂]²⁺ into interlocked architectures with efficient proton conduction[J]. Chinese Chemical Letters, ;2026, 37(11): 111698. doi: 10.1016/j.cclet.2025.111698 shu

Ligand-directed assembly of [Mo₂O₂S₂]²⁺ into interlocked architectures with efficient proton conduction

Liying Wang ^{a, 1} ,
Jiajia Li ^{b, 1} ,
Xin Liu ^a ,
Qianqian Liu ^a ,
Jiaxin Li ^a ,
Song Liang ^{c, *,} ,
Hong-Ying Zang ^{a, *,}

a.
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education at Universities of Jilin Province Faculty of Chemistry Northeast Normal University, Changchun 130024, China
b.
School of Chemistry and Environmental Engineering, Changchun University of Science and Technology, Changchun 130022, China
c.
Key Laboratory of Bionic Engineering of the Ministry of Education, College of Biological and Agricultural Engineering, Jilin University, Changchun 130022 China

songliang@jlu.edu.cn

zanghy100@nenu.edu.cn

Received Date: 8 July 2025
Revised Date: 2 August 2025
Accepted Date: 9 August 2025
Available Online: 10 August 2025

Figures(4)

As an important branch of polyoxometalates (POMs), polyoxothiometalates (POTMs) exhibit significant proton enrichment capabilities due to their high negative charge density and strong hydrophilicity. Their oxygen-rich surfaces provide an ideal platform for constructing long-range ordered hydrogen-bond networks, demonstrating unique advantages in proton conductor design. In this work, two novel POTM clusters based on [Mo₂O₂S₂]²⁺ building blocks were synthesized via an in situ strategy. Ligand and anionic template coordination modes critically direct structural assembly. Utilizing the AsO₄^3- template, with glyphosine (Gly) and 4,4′-sulfonyldibenzoic acid (H₂SDB) serving as bridging ligands to form dimeric structures: H₁₁K₄[(Co₃(AsO₄)₂(Mo₂O₂S₂)₆(OH)₆O₃(Gly)₃(H₂O)₅]·35H₂O (compound 1) and H₁₆K₄[(AsO₄)₄(Mo₂O₂S₂)₁₂(OH)₁₂O₄(H₂SDB)₆(H₂O)₂]·36H₂O (compound 2), with the latter exhibiting an edge-interlocking polyhedral architecture. Crystallography studies have shown that the rigid ligand H₂SDB in compound 2 significantly expands the framework porosity by geometrically fitting the {AsMo₆} unit, which has an inherent bending angle. To release the structural stress, two dimer construction units are vertically cross-linked after being rotated 180°, forming a unique edge-interlocking structure. Proton conduction measurements demonstrated that under conditions of 85 °C and 80% relative humidity, Compounds 1 and 2 exhibit proton conductivities of 9.64 × 10^-3 and 2.18 × 10^-2 S/cm, respectively, highlighting their significant potential as proton-conductive materials. This work provides a new strategy for the structure-oriented design of POM-based proton conductors.
- Polyoxometalates,
- [Mo₂O₂S₂]²⁺,
- Clusters,
- Self-assembly,
- Proton conduction
1. [1]
  J.L. Li, J.H. Wang, B.Y. Li, et al., Chin. Chem. Lett. 34 (2023) 107917. doi: 10.1016/j.cclet.2022.107917
2. [2]
  J.X. Ma, C. Wang, Q.Q. Liu, et al., Adv. Funct. Mater. 35 (2025) 2419752. doi: 10.1002/adfm.202419752
3. [3]
  J. Chang, G. Wang, W. Zhang, et al., J. Energy Chem. 68 (2022) 439-453. doi: 10.1016/j.jechem.2021.12.017
4. [4]
  A. Saha, R. Sahoo, S.C. Pal, et al., ACS Energy Lett. 10 (2025) 1958-1998. doi: 10.1021/acsenergylett.5c00373
5. [5]
  S.Y. Liu, X.X. Li, W.C. Chen, et al., Sci. China Chem. 67 (2024) 862-868. doi: 10.1007/s11426-023-1776-0
6. [6]
  H.Q. Jin, S.Y. Zou, X.C. Zhou, et al., Chin. Chem. Lett. 34 (2023) 107441. doi: 10.1016/j.cclet.2022.04.039
7. [7]
  I.E.L. Stephens, J. Rossmeisl, I. Chorkendorff, Science 354 (2016) 1378-1379. doi: 10.1126/science.aal3303
8. [8]
  J. Zuo, N.Y. Steiner, Z.L. Li, D. Hissel, Renew. Sustain. Energ. Rev. 201 (2024) 114613. doi: 10.1016/j.rser.2024.114613
9. [9]
  W.X. Zhang, S.Q. Zhao, R. Wang, et al., Adv. Compos. Hybrid Mater. 6 (2023) 60. doi: 10.2174/1381612829666221207112438
10. [10]
  A.L. Li, Q. Gao, J. Xu, X.H. Bu, Coord. Chem. Rev. 344 (2017) 54-82. doi: 10.1016/j.ccr.2017.03.027
11. [11]
  W. Liu, W. Mu, Y.L Deng, Angew. Chem. Int. Ed. 53 (2014) 13558-13562. doi: 10.1002/anie.201408226
12. [12]
  X. Cheng, C. Wang, J. Zhang, et al., Chem. Eng. J. 439 (2022) 135387. doi: 10.1016/j.cej.2022.135387
13. [13]
  S.C. Pal, M.C. Das, Adv. Funct. Mater. 31 (2021) 2101584. doi: 10.1002/adfm.202101584
14. [14]
  S.J. Wang, M. Wahiduzzaman, L. Davis, et al., Nat. Commun. 9 (2018) 4937. doi: 10.1038/s41467-018-07414-4
15. [15]
  R.B. Lin, Z.J. Zhang, B.L. Chen, Acc. Chem. Res. 54 (2021) 3362-3376. doi: 10.1021/acs.accounts.1c00328
16. [16]
  J. Chen, B. An, Y.L. Chen, et al., J. Am. Chem. Soc. 145 (2023) 19225-19231. doi: 10.1021/jacs.3c03943
17. [17]
  K. Otsubo, S. Nagayama, S. Kawaguchi, et al., JACS Au 2 (2022) 109-115. doi: 10.1021/jacsau.1c00388
18. [18]
  M. Boone, F. Artizzu, J. Goura, et al., Coord. Chem. Rev. 501 (2024) 215525. doi: 10.1016/j.ccr.2023.215525
19. [19]
  L.Y. Zhu, L.M. Zhang, Y.T. Ren, et al., Adv. Funct. Mater. 34 (2024) 2313844. doi: 10.1002/adfm.202313844
20. [20]
  L. Liu, L.Y. Yin, D.M. Cheng, et al., Angew. Chem. Int. Ed. 60 (2021) 14875-14880. doi: 10.1002/anie.202104106
21. [21]
  M. Lupa-Myszkowska, M. Oszajca, D. Matoga, Chem. Sci. 14 (2023) 14176-14181. doi: 10.1039/d3sc04401g
22. [22]
  Y.Y. Sun, J. Wei, Z.H. Fu, et al., Adv. Mater. 35 (2023) 2208625. doi: 10.1002/adma.202208625
23. [23]
  Q.Y. Hu, S.S. Chen, T. Wågberg, et al., Angew. Chem. Int. Ed. 62 (2023) e202303290. doi: 10.1002/anie.202303290
24. [24]
  Q.Y. Hu, H.S. Zhou, Y. Ding, et al., ACS Catal. 14 (2024) 5898-5910. doi: 10.1021/acscatal.4c00201
25. [25]
  Y. Gao, A.M. Nolan, P. Du, et al., Chem. Rev. 120 (2020) 5954-6008. doi: 10.1021/acs.chemrev.9b00747
26. [26]
  D.W. Lim, H. Kitagawa, Chem. Rev. 120 (2020) 8416-8467. doi: 10.1021/acs.chemrev.9b00842
27. [27]
  S. Bureekaew, S. Horike, M. Higuchi, et al., Nat. Mater. 8 (2009) 831-836. doi: 10.1038/nmat2526
28. [28]
  Y.F. Liu, J.W. Cao, J. Wu, et al., Inorg. Chem. 64 (2025) 12619-12626. doi: 10.1021/acs.inorgchem.5c01101
29. [29]
  H.Y. Wang, D.D. Zhang, J.Y. Niu, et al., Chin. Chem. Lett. 35 (2024) 108486. doi: 10.1016/j.cclet.2023.108486
30. [30]
  B.W. Li, T. Wang, M. Xu, et al., Chin. Chem. Lett. 36 (2025) 110467. doi: 10.1016/j.cclet.2024.110467
31. [31]
  N. Ogiwara, T. Iwano, T. Ito, S. Uchida, Coord. Chem. Rev. 462 (2022) 214524. doi: 10.1016/j.ccr.2022.214524
32. [32]
  X.Y. Wang, M.Y. Cheng, Y.N. Liu, et al., Inorg. Chem. 64 (2025) 11561-11570. doi: 10.1021/acs.inorgchem.5c00919
33. [33]
  X. Bai, X. Han, Y.X. Wang, et al., Inorg. Chem. 62 (2023) 13221-13229. doi: 10.1021/acs.inorgchem.3c01393
34. [34]
  G. Kalandia, C.L. Liu, D.E. Salazar Marcano, et al., Angew. Chem. Int. Ed. 64 (2025) e202420773. doi: 10.1002/anie.202420773
35. [35]
  Q.X. Zhao, Y. Zeng, Z.Q. Jiang, et al., Angew. Chem. Int. Ed. 64 (2025) e202421132. doi: 10.1002/anie.202421132
36. [36]
  Q. Zhu, Z.H. Li, T. Zheng, et al., Angew. Chem. Int. Ed. 64 (2025) e202413594. doi: 10.1002/anie.202413594
37. [37]
  J.C. Luo, K. Chen, P.C. Yin, et al., Angew. Chem. Int. Ed. 57 (2018) 4067-4072. doi: 10.1002/anie.201800409
38. [38]
  G.P. Yang, J.W. Cao, Y. Xiao, et al., Inorg. Chem. 64 (2025) 1041-1047. doi: 10.1021/acs.inorgchem.4c04468
39. [39]
  G.P. Yang, H.Q. Liu, S.H. Zhang, et al., Inorg. Chem. 63 (2024) 22955-22961. doi: 10.1021/acs.inorgchem.4c04086
40. [40]
  Z.F. Lin, G.P. Yang, W.J. Jiang, et al., Inorg. Chem. 63 (2024) 19390-19395. doi: 10.1021/acs.inorgchem.4c03346
41. [41]
  H.Y. Zang, H.N. Miras, J. Yan, et al., J. Am. Chem. Soc. 134 (2012) 11376-11379. doi: 10.1021/ja304371j
42. [42]
  B. Li, X.Z. Duan, Y.Z. Cui, et al., Angew. Chem. Int. Ed. 36 (2024) e202408096. doi: 10.1002/anie.202408096
43. [43]
  H.Y. Zang, A.R. Oliva, H.N. Miras, et al., Nat. Commun. 5 (2014) 3715. doi: 10.1038/ncomms4715
44. [44]
  B. Li, X.Z. Duan, D.M. Cheng, et al., J. Am. Chem. Soc. 145 (2023) 2243-2251. doi: 10.1021/jacs.2c10225
45. [45]
  E. Cadot, M.N. Sokolov, V.P. Fedin, et al., Chem. Soc. Rev. 41 (2012) 7335-7353. doi: 10.1039/c2cs35145e
46. [46]
  W.J. Liu, Y.Q. Lan, et al., ACS Appl. Mater. Interfaces 11 (2019) 7030-7036. doi: 10.1021/acsami.8b20509
47. [47]
  B. Li, Q.Q. Liu, H.Y. Zang, et al., Chem. Commun. 59 (2023) 13446. doi: 10.1039/d3cc04114j
48. [48]
  X. Yu, Y.H. Gu, S. Yuan, et al., Dalton Trans. 53 (2024) 17902-17908. doi: 10.1039/d4dt02609h
49. [49]
  G.P. Yang, H.J. Shi, Z.F. Lin, et al., Inorg. Chem. 63 (2024) 19039-19045. doi: 10.1021/acs.inorgchem.4c03662
50. [50]
  J.W. Zhang, Z.H. Liu, Y.C. Huang, et al., Chem. Commun. 51 (2015) 9097-9100. doi: 10.1039/C5CC02947C
51. [51]
  G.Y. Dai, Q. Li, D.J. Zang, Y.G. Wei, Green Chem. 25 (2023) 6263-6269. doi: 10.1039/d3gc00951c
52. [52]
  W.R. Deng, Z.H. Zhu, Y.J. Sun, et al., Polyoxometalates 3 (2024) 9140071. doi: 10.26599/pom.2024.9140071
53. [53]
  Q.Q. Shang, K.Q. Shen, D.Y. Zhao, et al., Polyoxometalates 4 (2025) 9140077. doi: 10.26599/pom.2024.9140077
54. [54]
  B. Hu, Q.C. Du, Y. Yang, et al., Polyoxometalates 4 (2025) 9140079. doi: 10.26599/pom.2024.9140079
55. [55]
  X.X. Li, C.H. Li, M.J. Hou, et al., Nat. Commun. 14 (2023) 5025. doi: 10.1038/s41467-023-40685-0
56. [56]
  W. Ma, J. Jin, X. Huang, et al., Dalton Trans. 49 (2020) 3849-3855. doi: 10.1039/c9dt04333k
57. [57]
  R.L. Liu, Y.F. Chen, X. Su, et al., Coord. Chem. Rev. 522 (2025) 216224. doi: 10.1016/j.ccr.2024.216224
58. [58]
  H.K. Guo, L.B. Li, X.L. Xu, et al., Angew. Chem. Int. Ed. 61 (2022) e202210695. doi: 10.1002/anie.202210695
59. [59]
  B. Wang, R.B. Lin, Z.J. Zhang, et al., J. Am. Chem. Soc. 142 (2020) 14399-14416. doi: 10.1021/jacs.0c06473
60. [60]
  T. Miruszewski, K. Dzierzgowski, P. Winiarz, et al., J. Mater. Chem. A 10 (2022) 7218-7227. doi: 10.1039/d1ta10916b
1. [1]
  Qianqian Liu , Jianxin Ma , Lian Xiao , Shilei Liu , Yongzhen Chen , Liying Wang , Yunzuo Cui , Song Liang , Hong-Ying Zang . Controlled assembly of phosphonic acid ligand covalently modified [TeMo₆O₂₁]^2- polyanions for proton conduction. Chinese Chemical Letters, 2026, 37(9): 111413-. doi: 10.1016/j.cclet.2025.111413
2. [2]
  Jiajia Li , Liying Wang , Qianqian Liu , Shuang Yu , Hong-Ying Zang , Zhong-Min Su . Ln³⁺/Bi³⁺-induced the assembly of molybdenum-oxygen clusters with proton conductivity. Chinese Chemical Letters, 2026, 37(10): 111532-. doi: 10.1016/j.cclet.2025.111532
3. [3]
  Yingjie Li , Hailong Hu , Aoqi Wang , Jingru Huang , Shiqi Fu , Zongyin Gao , Shuo Tao , Yalin Zhang , Qingde Zhang , Haitao Wang , Xianqiang Huang . Hetero-motif POM molecular junctions enable tandem olefin epoxidation and CO2 fixation. Chinese Journal of Structural Chemistry, 2026, 45(8): 100946-100946. doi: 10.1016/j.cjsc.2026.100946
4. [4]
  Teng-Fei Yao , Guo-Ping Yang , Yao-Yu Wang . Boosting efficient electrocatalytic CO2 reduction by two-dimensional polyoxometalate@metal-organic framework composites with asymmetric sites. Chinese Journal of Structural Chemistry, 2026, 45(8): 100948-100948. doi: 10.1016/j.cjsc.2026.100948
5. [5]
  Yongzhen Chen , Jianxin Ma , Yuyang Wang , Qianqian Liu , Yunzuo Cui , Weibo Ren , Chen Wang , Zhong-Min Su , Hong-Ying Zang . Modulator-driven structural expansion: From 2D copper coordination polymer to 3D MOF with enhanced proton conductivity. Chinese Chemical Letters, 2026, 37(8): 111266-. doi: 10.1016/j.cclet.2025.111266
6. [6]
  Hanhan Chen , Yahao Sun , Mingyang Zhang , Pengtao Ma , Jingping Wang , Jingyang Niu . Self-assembly of cis-trans Ta/W mixed-addendum POMs based on hexalacunary [H₂P₂W₁₂O₄₈]¹²⁻ building blocks. Chinese Chemical Letters, 2025, 36(9): 110329-. doi: 10.1016/j.cclet.2024.110329
7. [7]
  Wanting Sun , Lan Deng , Mengyun Zhao , Tianfu Liu , Hongjin Lv . Controllable syntheses of {SbW₉O₃₃}-sandwiched silver clusters induced by external phosphine ligands towards 4-nitrophenol reduction. Chinese Chemical Letters, 2026, 37(9): 111416-. doi: 10.1016/j.cclet.2025.111416
8. [8]
  Fei Li , Yibin Sun , Bao Li , Siyuan Xu , Shuangyu Wu , Lixin Wu , Guanglu Wu . Portal-directed assembly of 2D cucurbituril-polyoxometalate hybrids toward synergistic photothermal catalysis. Chinese Chemical Letters, 2026, 37(8): 112034-. doi: 10.1016/j.cclet.2025.112034
9. [9]
  Chunhui Wang , Zhe Han , Yuan Gao , Chaoyue Fan , Puyong He , Bojun Li , Dong Ma , Yang Zhang , Lei Zhang , Jie Qiu . Aluminate-mediated assembly of Keggin-type thorium-oxo clusters with a substitutable central octahedron and tunable shell ligands. Chinese Chemical Letters, 2026, 37(10): 111563-. doi: 10.1016/j.cclet.2025.111563
10. [10]
  Kun Zhang , Lei Wu , Kaixi Lan , Yanting Zhang , Wenxin Zhang , Huanhuan Li , Guoji Huang , Dongshuang Wu , Long Chen , Manni Li . N-3 of 1-methylimidazole: Enhancing proton conduction in COF under humidity conditions. Chinese Chemical Letters, 2026, 37(6): 111043-. doi: 10.1016/j.cclet.2025.111043
11. [11]
  Yi Chen , Hua-Pan Wu , Zheng-Wei Guo , Xin-Xiong Li , Ping-Wei Cai , Shou-Tian Zheng . Construction of a diverting polyoxotungstate based on 3d-5p heterometallic cluster for high-performance single-crystal proton conduction. Chinese Chemical Letters, 2025, 36(11): 110552-. doi: 10.1016/j.cclet.2024.110552
12. [12]
  Tiantian Gong , Yanan Chen , Shuo Wang , Miao Wang , Junwei Zhao . Rigid-flexible-ligand-ornamented lanthanide-incorporated selenotungstates and photoluminescence properties. Chinese Journal of Structural Chemistry, 2024, 43(9): 100370-100370. doi: 10.1016/j.cjsc.2024.100370
13. [13]
  Yuanpeng Ye , Longfei Yao , Guofeng Liu . Engineering circularly polarized luminescence through symmetry manipulation in achiral tetraphenylpyrazine structures. Chinese Journal of Structural Chemistry, 2025, 44(2): 100460-100460. doi: 10.1016/j.cjsc.2024.100460
14. [14]
  Jiaye Wang , Xiong Yang , Yang Lei , Tianwen Xi , Sijie Wang , Yidan Zhou , Bing Liu , Yu Liu , Hui Yang , Leming Sun . Zinc coordination self-assembly of bacitracin nanoparticles with broadened antibacterial spectrum. Chinese Chemical Letters, 2026, 37(4): 111086-. doi: 10.1016/j.cclet.2025.111086
15. [15]
  Tengteng Wang , Yiming Ju , Yao Cheng , Haiyang Wang , Dejin Zang . Recent advances in polyoxometalates based strategies for green synthesis of drugs. Chinese Chemical Letters, 2025, 36(5): 109871-. doi: 10.1016/j.cclet.2024.109871
16. [16]
  Zhihan Chang , Yuchen Zhang , Yuan Tian , Xiuli Wang . Achieving high-proportioned 1T-MoS₂ within heterostructures derived from polymolybdate-based complex for boosting electrocatalytic hydrogen evolution and oxygen evolution. Chinese Chemical Letters, 2025, 36(8): 110197-. doi: 10.1016/j.cclet.2024.110197
17. [17]
  Sifan Du , Yuan Wang , Fulin Wang , Tianyu Wang , Li Zhang , Minghua Liu . Evolution of hollow nanosphere to microtube in the self-assembly of chiral dansyl derivatives and inversed circularly polarized luminescence. Chinese Chemical Letters, 2024, 35(7): 109256-. doi: 10.1016/j.cclet.2023.109256
18. [18]
  Hao Zhang , Hao Liu , Ke Huang , Qingxiu Xia , Hongjie Xiong , Xiaohui Liu , Hui Jiang , Xuemei Wang . Ionic exchange based intracellular self-assembly of pitaya-structured nanoparticles for tumor imaging. Chinese Chemical Letters, 2025, 36(6): 110281-. doi: 10.1016/j.cclet.2024.110281
19. [19]
  Guoping Yang , Zhoufu Lin , Xize Zhang , Jiawei Cao , Xuejiao Chen , Yufeng Liu , Xiaoling Lin , Ke Li . Assembly of Y(Ⅲ)-containing antimonotungstates induced by malic acid with catalytic activity for the synthesis of imidazoles. Chinese Chemical Letters, 2024, 35(12): 110274-. doi: 10.1016/j.cclet.2024.110274
20. [20]
  Yuwen Zhu , Xiang Deng , Yan Wu , Baode Shen , Lingyu Hang , Yuye Xue , Hailong Yuan . Formation mechanism of herpetrione self-assembled nanoparticles based on pH-driven method. Chinese Chemical Letters, 2025, 36(1): 109733-. doi: 10.1016/j.cclet.2024.109733

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(36)
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

Ligand-directed assembly of [Mo2O2S2]2+ into interlocked architectures with efficient proton conduction

Metrics

通讯作者: 陈斌, bchen63@163.com

Ligand-directed assembly of [Mo₂O₂S₂]²⁺ into interlocked architectures with efficient proton conduction