| 咪唑鎓盐功能化锆基金属有机笼的合成及其主客体性质 |
| Synthesis and host-guest properties of imidazolium-functionalized zirconium metal-organic cage |
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| 摘要: 设计并合成了咪唑鎓盐官能化的羧酸配体(H2L)Cl(1，3-bis[4'-carboxy-3，5-dimethyl-(1，1'-biphenyl)-4-yl]-imidazolium chlo-ride)，并使其与二氯二茂锆(Cp2ZrCl2，Cp=η5-C5H5)反应，制备了咪唑鎓盐功能化的锆基金属有机笼[(Cp3Zr3)2(L)3]Cl5(MOC-1)，其中Cp3Zr3=(CpZr)3(μ3-O)(μ2-OH)3。利用单晶X射线衍射、核磁共振氢谱、电喷雾电离质谱、紫外可见吸收光谱、红外光谱、热重分析等测试手段对MOC-1进行表征。单晶X射线衍射分析表明，MOC-1的阳离子骨架由2个Cp3Zr3单元和3个L-配体组成。通过核磁氢谱研究了MOC-1与不同体积大小的芳基磺酸根阴离子之间的主客体性质。结果表明，与体积较大的芳基磺酸根阴离子G4(对乙基苯磺酸根)和G5(对异丙基苯磺酸根)相比，MOC-1与空腔匹配度更高的G1~G3(分别为苯磺酸根、对氯苯磺酸根、对甲基苯磺酸根)之间的主客体相互作用更强。 |
| 关键词: 咪唑鎓盐 锆基金属有机笼 主客体化学 |
| 基金项目: 河南省教育厅高等学校重点科研项目计划(No.24A150049)、国家级大学生创新创业训练计划(No.202310478038)、周口师范学院高层次人才科研启动项目(No.ZKNUC2021015)和国家自然科学基金项目(No.22025107)资助。 |
| Abstract: 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). |
| Keywords: imidazolium salt zirconium metal-organic cage host-guest chemistry |
| 投稿时间：2024-10-09 修订日期：2024-11-21 |
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| 石文杰,陆凡,陈梦薇,王进,韩英锋.咪唑鎓盐功能化锆基金属有机笼的合成及其主客体性质[J].无机化学学报,2025,41(1):105-113. |
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