Citation: Wenjie SHI, Fan LU, Mengwei CHEN, Jin WANG, Yingfeng HAN. Synthesis and host-guest properties of imidazolium-functionalized zirconium metal-organic cage[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(1): 105-113. doi: 10.11862/CJIC.20240360 shu

Synthesis and host-guest properties of imidazolium-functionalized zirconium metal-organic cage

Wenjie SHI ¹ ,
Fan LU ¹ ,
Mengwei CHEN ¹ ,
Jin WANG ¹ ,
Yingfeng HAN ^2,,

1.
School of Chemistry and Chemical Engineering, Zhoukou Normal University, Zhoukou, Henan 466001, China
2.
College of Chemistry & Materials Science, Northwest University, Xi′an 710127, China

Corresponding author: Yingfeng HAN, yfhan@nwu.edu.cn
Received Date: 9 October 2024
Revised Date: 21 November 2024

Figures(7)

An imidazolium-functionalized carboxylic acid ligand (H₂L)Cl (1, 3-bis[4′-carboxy-3, 5-dimethyl-(1, 1′-biphenyl)-4-yl]-imidazolium chloride) was designed and synthesized. An imidazolium-functionalized zirconium metal-organic cage [(Cp₃Zr₃)₂(L)₃]Cl₅ (MOC-1), where Cp₃Zr₃=(CpZr)₃(μ₃-O)(μ₂-OH)₃ and Cp=η⁵-C₅H₅, was prepared by the reaction of (H₂L)Cl with bis(cyclopentadienyl)zirconium dichloride (Cp₂ZrCl₂). MOC-1 was characterized by single-crystal X-ray diffraction, ¹H NMR, electrospray ionization-mass spectrometry, UV-Vis absorption spectrum, IR spectroscopy, thermogravimetric analysis, and other test methods. Single-crystal X-ray diffraction analysis demonstrates the cationic skeleton of MOC-1 consists of two Cp₃Zr₃ units and three L^- ligands. The three imidazole groups are located in the middle of the cage and point towards the inside. MOC-1 exhibits a cavity in an irregular pentagonal bipyramidal shape. The host-guest properties between MOC-1 and aryl sulfonate anions of different sizes were studied by ¹H NMR. The results show that the host-guest interaction between MOC-1 and G¹-G³ (benzenesulfonate, p-chlorophenyl sulfonate, and p-methyl benzenesulfonate, respectively) with better cavity matching was stronger than that between the larger aryl sulfonate anions G⁴ (p-ethyl benzenesulfonate) and G⁵ (p-isopropyl benzenesulfonate).
- imidazolium salt,
- zirconium metal-organic cage,
- host-guest chemistry
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