三氮唑冠醚型超分子功能材料的合成及性能研究

Study on synthesis and performance of triazole&crown ether-based supramolecular functional materials

以三唑类化合物4-氨基-1,2,4-三氮唑、18-冠醚-6和高氯酸为原料,获得一种新型的有机-无机杂化功能材料(18-crown-6)(C_(2)H_(2)N_(3)N_(H)_(3))(C10_(4))(1)。对其进行了红外光谱、单晶X射线衍射、介电常数、热重(TG)、粉末X射线衍射(XRD)等分析测试,由单晶X射线衍射测试结果表明,该化合物在低温和室温下空间群均为C2/c,属于单斜晶系,晶胞内(C_(2)H_(2)N_(3)NH_(3))^(+)阳离子结构呈现有序-无序运动,质子化的4-氨基-1,2,4-三氮唑离子通过氢键相互作用镶嵌入18-冠醚-6环内,在c轴形成一维链状超分子结构。通过变温变频介电测试发现化合物1在a、c轴方向上240~280 K温度范围内产生明显的介电异常,这可能是有机阳离子及无机阴离子发生分子运动导致的。

A novel organic-inorganic hybrid functional material(18-crown-6)(C_(2)H_(2)N_(3)NH_(3))(C10_(4))(1) was synthesized from triazole compounds 4-amino-1,2,4-triazole,18-crown-6 and perchloric acid.The infrared spectrum,single crystal X-ray diffraction,dielectric constant,thermogravimetric(TG),powder X-ray diffraction(XRD) and other analysis tests were carried out.The results of single crystal X-ray diffraction test showed that the space group of the compound was C2/c at low temperature(100 K) and room temperature(296 K),belonging to the monocline crystal system.Intracellular(C_(2)H_(2)N_(3) NH_(3))~+cationic structure exhibited order-disorder motion,and protonated 4-amino-1,2,4-triazole ions were embedded into the 18-crown-6 ring through N-H…O hydrogen bond interaction,forming a one-dimensional chain supramolecular structure on the c axis.It was found that compound 1 produced obvious dielectric anomaly in the temperature range of 240~280 K along the a and c axis,which might be caused by the molecular movement of organic cations and inorganic anions.