两个基于多金属氧酸盐和冠醚基超分子阳离子的有机无机杂化材料的合成及晶体结构 |
Two Inorganic-Organic Hybrid Crystals Based on Polyoxometallates and Supramolecular Cation:Syntheses and Crystal Structures |
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摘要: 以二苯并18-冠-6,3-氟-4-甲基苯铵盐以及多金属氧酸盐[Mo6O19]2-为原料,使用溶剂挥发法合成了有机无机杂化材料[(3-F-4-MeAnis)(DB[18]crown-6)]2[Mo6O19]·2CH3CN (1)(3-F-4-MeAnis=3-氟-4-甲基苯铵盐;DB[18]crown-6=二苯并18-冠-6);以18-冠-6,2-氟-4-甲基苯铵盐以及多金属氧酸盐[SMo12O40]2-为原料,运用H管扩散法制备了晶体材料[(2-F-4-MeAnis)([18]crown-6)]2[SMo12O40]·2CH3CN (2)(2-F-4-MeAnis=2-氟-4-甲基苯铵盐;[18]crown-6=18-冠-6)。通过红外光谱、元素分析、热重分析和X射线单晶结构分析对化合物进行了表征。结构分析表明,晶体1和2通过非共价键自组装作用构建而成,冠醚基超分子阳离子是通过N-H…O氢键作用形成。在晶体1和2中,超分子阳离子和多酸阴离子交错堆积形成包合物结构,沿着a轴方向观察,发现每个多酸阴离子被6个超分子阳离子包围着形成六边形堆积结构。通过晶体结构研究和热重分析表明,二苯并18-冠-6中的苯环在维持晶体1的稳定性方面具有重要的作用。 |
关键词: 有机无机杂化物 超分子自组装 多金属氧酸盐 冠醚 超分子阳离子 |
基金项目: 武汉纺织大学未来之星助推计划(No.165002)资助项目。 |
Abstract: Two new inorganic-organic hybrids[(3-F-4-MeAnis)(DB[18]crown-6)]2[Mo6O19]·2CH3CN (1) and[(2-F-4-MeAnis)([18]crown-6)]2[SMo12O40]·2CH3CN (2) (3-F-4-MeAnis=3-fluoro-4-methylanilinium, DB[18]crown-6=dibenzo[18]crown-6,2-F-4-MeAnis=2-fluoro-4-methylanilinium) have been synthesized and characterized by infrared spectrum (IR), elemental analysis (EA), thermosgravimetric analysis (TGA) and X-ray diffraction. Compounds 1 and 2 are constructed through noncovalent bonding interaction and the polyoxometalates (POMs) and supramolecular cation arrange alternately. Supramolecular cation forms through the N-H…O hydrogen bonding interaction between the nitrogen atom of anilinium and oxygen atoms of crown ether derivatives. In the crystals of 1 and 2, each polyoxoanion is surrounded by six supramolecular cations and forms hexagonal arrangement viewed along the a axis. Crystalline structure and TGA indicated that phenyl rings in DB[18]crown-6 plays an important role in maintaining the stability of compound 1. |
Keywords: inorganic-organic hybrids supramolecular self-assembled polyoxometallates crown ether supramolecular cation |
投稿时间:2017-03-31 修订日期:2017-05-17 |
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熊俊,吕少仿,彭俊军,李明,李伟,杨水彬.两个基于多金属氧酸盐和冠醚基超分子阳离子的有机无机杂化材料的合成及晶体结构[J].无机化学学报,2017,33(9):1649-1655. |
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