Citation: Mengyu LI, Kewei TONG, Li ZHANG, Minghua LU, Abudula, Luwen ZHU, Yi LIU, Luying WANG, Baiqiao SONG, Zunqi LIU, Peng YANG, Yanhu WANG. Functionalizing the cavities of imidazolyl polyoxovanadate‒organic polyhedra with embedded pyridine to modulate iodine adsorption[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(9): 1974-1983. doi: 10.11862/CJIC.20260154 shu

Functionalizing the cavities of imidazolyl polyoxovanadate‒organic polyhedra with embedded pyridine to modulate iodine adsorption

Figures(6)

  • Two functionalized polyoxovanadate-organic polyhedra (VMOPs) were successfully constructed by directed assembly of an imidazolyl-functionalized ligand 4,4′,4″-(1H-imidazole-2,4,5-triyl)tribenzoic acid (H3ITTA) with two distinct 3-connected vanadate clusters: [V6ⅣO6(OCH3)9(SO4)(CO2)3]2- ({V6S}) afforded (TMA)8{[V6O6(OCH3)9(SO4)]4(ITTA)4}·17CH3OH·20DMF (TMA-VMOT-S-1) with a pristine cavity (TMA+=(CH3)4N+), while [V6ⅣO6(OCH3)9 (PyPO3)(CO2)3]2- ({V6P}) yielded (TMA)8{[V6O6(OCH3)9(PyPO3)]4(ITTA)4}·26CH3OH·8DMF (TMA-VMOT-P-1) containing a pyridn-4-ylposphonic acid (PyPO3H2) moiety embedded within the cavity. The two compounds were systematically characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. Structural analysis revealed that cavity functionalization causes a slight expansion of the cage architecture of TMA-VMOT-P-1, accompanied by a reduction in its effective cavity volume. Despite these structural differences, both VMOPs displayed similar iodine adsorption capacity and kinetics, attributable to the synergistic interplay between the cavity architecture and the embedded functional sites. This work establishes that both cavity dimensions and embedded functional groups are pivotal for iodine capture.
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