Citation: 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[J]. Chinese Chemical Letters, ;2026, 37(9): 111413. doi: 10.1016/j.cclet.2025.111413 shu

Controlled assembly of phosphonic acid ligand covalently modified [TeMo₆O₂₁]^2- polyanions for proton conduction

Qianqian Liu ^{a, 1} ,
Jianxin Ma ^{b, 1} ,
Lian Xiao ^{a, 1} ,
Shilei Liu ^a ,
Yongzhen Chen ^c ,
Liying Wang ^a ,
Yunzuo Cui ^a ,
Song Liang ^{c, *,} ,
Hong-Ying Zang ^{a, *,}

a.
Key Laboratory of Polyoxometalate and Reticular Chemistry of Ministry of Education 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: 15 April 2025
Revised Date: 27 May 2025
Accepted Date: 6 June 2025
Available Online: 6 June 2025

Figures(4)

Achieving higher proton conductivity of proton-conducting materials in solid-state is one of the utmost challenges in materials science. Due to their oxygen-rich structure and negative surface charge, polyoxometalates (POMs) anions have high requirements for proton carrier density and proton mobility, and thus have great potential as proton conducting materials. Furthermore, the versatility in modifying the ligand environment or incorporating acidic functional groups in POMs allows for precise tuning of their proton conductivity and stability under operational conditions. Therefore, it is an effective strategy to select a suitable organic ligand to stabilize the [TeMo₆O₂₁]^2- anion assembled in-situ by covalent modification. In this paper, three [TeMo₆O₂₁]^2- anionic clusters have been designed and synthesized by using polydentate phosphonate ligands and guided by transition metals, H₂₆[Co₆{N(CH₂PO₃)₂(CH₂COO)}₆(TeMo₆O₂₁)₄(H₂O)₈]·64H₂O (complex 1), H₂₆[Cu₆{N(CH₂PO₃)₂(CH₂COO)}₆(TeMo₆O₂₁)₄(H₂O)₆]·78H₂O (complex 2) and H₃₄Na₂[Co₈{N₂(CH₂)₂(CH₂PO₃)₃(CH₂PO₃H₂)}₄(TeMo₆O₂₁)₆(PO₃)₄(H₂O)₁₆]·84H₂O (complex 3). Among them, complexes 1 and 2 are isomorphic, and complexes 1–3 have good proton conduction properties, resulting in values of 1.3 × 10⁻², 1.22 × 10⁻², and 1.11 × 10⁻² S/cm, respectively (75% relative humidity, 80 ℃). This work offers a promising strategy for the development and design of novel telluromolybdate clusters suitable for proton conductive materials.
- Polyoxometalates,
- Clusters,
- In-situ synthesis,
- Covalent modification,
- Proton conduction
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Controlled assembly of phosphonic acid ligand covalently modified [TeMo6O21]2- polyanions for proton conduction

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Controlled assembly of phosphonic acid ligand covalently modified [TeMo₆O₂₁]^2- polyanions for proton conduction