Demko-Sharpless 合成稀土四唑化合物的结构及性质

摘要/Abstract

摘要： 使用 Demko-Sharpless法,用氰基吡啶(4-氰基吡啶和3-氰基吡啶)与稀土硝酸盐(Ln=La, Gd, Er)在水热条件下反应,安全有效地合成了四个稀土四唑离子型化合物:[Ln(H₂O)₈·3(p-TPD)·2(p-HTPD)·7H₂O], (Ln=La(1), Gd(2), Er(3), p-TPD=4-四唑吡啶), [Ln(H₂O)₈·3(m-TPD)·6H₂O]和(m-TPD=3-四唑吡啶, Ln=Er(4))。同时,对这四个稀土四唑离子型化合物进行单晶X射线衍射、红外光谱、热重、介电性能、X射线粉末衍射等测试,并且对其介电性质进行了研究。X射线单晶结构分析显示,所得到的四个稀土四唑化合物均为离子型,稀土金属离子与配体分别处于不同的两层,[Ln(H₂O)₈]³⁺结构单元与 p-TPD 以及水分子通过氢键作用形成阳离子层,同时p-TPD与p-HTPD通过π-π堆积与氢键作用形成阴离子层,阳离子层和阴离子层交替排列形成一个规则的网络结构。介电性能测试表明化合物1,2具有较好的介电性。

关键词: 四唑化合物, 稀土硝酸盐, 晶体结构, 热重分析, 介电性能

Abstract: The tetracyanopyridine (4-cyanopyridine and 3-cyanopyridine) was reacted with rare earth nitrates (Ln=La, Gd, Er) under hydrothermal conditions by the Demko-Sharpless method, and four rare earth tetrazolium ionic compound were synthesized safely and effectively, named [Ln(H₂O)₈·3(p-TPD)·2(p-HTPD)·7H₂O], (Ln=La(1), Gd(2), Er(3), p-TPD=4-tetrazolpyridine), [Ln(H₂O)₈·3(m-TPD)·6H₂O], (m-TPD=3-tetrazolpyridine, Ln=Er(4)). These four rare earth tetrazolium ionic compounds were characterized by the single crystal X-ray diffraction, infrared spectroscopy, thermogravimetry, dielectric properties, X-ray powder diffraction. The X-ray single crystal structure analysis shows that the four rare earth tetrazolium compounds were all ionic, and the rare earth metal ions and ligands were in two different layers. The [Ln(H₂O)₈]³⁺ structure unit and p-TPD and water molecules formed a cationic layer through hydrogen bonding, while p-TPD and p-HTPD formed an anion layer through π-π stacking and hydrogen bonding. The cation layer and anion layer alternately form a regular network structure. Moreover, the dielectric properties tests indicate that the compounds 1, 2 have good dielectric properties.

Key words: tetrazole compound, rare earth nitrate, crystal structure, TGA, dielectric property

中图分类号:

O641.4

应婷婷, 韩定冲, 谭育慧, 李玉孔, 黄珺, 唐云志, 杜鹏康, 庄加昌. Demko-Sharpless 合成稀土四唑化合物的结构及性质[J]. 人工晶体学报, 2021, 50(8): 1464-1470.

YING Tingting, HAN Dingchong, TAN Yuhui, LI Yukong, HUANG Jun, TANG Yunzhi, DU Pengkang, ZHUANG Jiachang. Synthesis, Structures and Properties of Tetrazole Compounds by Demko-Sharpless Method[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(8): 1464-1470.

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