Citation: Wei LI, Jianjie XU, Linlin WANG, Chuanbing HOU, Hongliang HAN, Qionghua JIN. Synthesis, structure, and photocatalytic properties of {PMo₁₂}-based rare-earth tetraisopropyl ethylenediphosphonate complexes[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(10): 2077-2091. doi: 10.11862/CJIC.20260220 shu

Synthesis, structure, and photocatalytic properties of {PMo₁₂}-based rare-earth tetraisopropyl ethylenediphosphonate complexes

Wei LI ¹ ,
Jianjie XU ¹ ,
Linlin WANG ² ,
Chuanbing HOU ² ,
Hongliang HAN ¹ ,
Qionghua JIN ^{1, 3, 4,,}

1.
Department of Chemistry, Capital Normal University, Beijing 100048, China
2.
School of Resources, Environment and Tourism, Capital Normal University, Beijing 100048, China
3.
Shanghai Key Laboratory of Chemical Assessment and Pollution Control, Tongji University, Shanghai 200092, China
4.
State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210023, China

Corresponding author: Qionghua JIN, jinqh204@163.com; jinqh@cnu.edu.cn
Received Date: 12 July 2026
Revised Date: 11 September 2026

Figures(18)

Using Keggin-type phosphomolybdic acid (H₃PMo₁₂O₄₀) as the template and tetraisopropyl ethylenediphosphonate (L) as the neutral bidentate chelating ligand, four rare-earth complexes [Ln(L)₃(H₂O)₂](PMo₁₂O₄₀)·4CH₃CN (Ln=Pr, Tb, Dy, Er) were synthesized via a water-bath reflux method. The complexes were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and solid-state UV-Vis diffuse reflectance spectroscopy. Single-crystal structure determination revealed that the four complexes are isostructural and crystallize in the triclinic space group P1. Each central Ln³⁺ ion adopts an eight-coordinate distorted square-antiprism geometry, coordinated by three bidentate chelating L ligands and two water molecules. The polyoxometalate anions serve as counterions and are held in the lattice via hydrogen bonds. Thermogravimetric analysis recorded three-stage mass-loss processes for all complexes. The optical band gaps, calculated from solid-state UV-Vis diffuse reflectance spectra, were 2.56-2.57 eV. Photocatalytic degradation experiments of the complexes on rhodamine B showed degradation rates of 95.21%-97.53% within 90 min of UV irradiation. Radical trapping experiments identified ·OH, ·O₂^- and h⁺ as the reactive species participating in the photocatalytic process. Terahertz time-domain spectroscopy (0.4-2.4 THz) recorded characteristic absorption peaks arising from ligand skeleton vibrations and intermolecular weak interactions, with spectral profiles remaining largely unchanged across the four lanthanide centers.
- polyoxometalate,
- rare-earth complex,
- tetraisopropyl ethylenediphosphonate,
- photocatalysis,
- rhodamine B,
- terahertz spectroscopy
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Synthesis, structure, and photocatalytic properties of {PMo12}-based rare-earth tetraisopropyl ethylenediphosphonate complexes

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通讯作者: 陈斌, bchen63@163.com

Synthesis, structure, and photocatalytic properties of {PMo₁₂}-based rare-earth tetraisopropyl ethylenediphosphonate complexes