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利用氰基吡啶(4-氰基吡啶和3-氰基吡啶)与稀土硝酸盐作用(Ln=Nd,Eu,Yb),通过原位[2+3]环加成反应合成得到了4个稀土四唑离子型化合物,Ln(H2O)8·3(p-TPD)·2(p-HTPD)·7H2O),(Ln=Nd(1),Eu(2),Yb(3)),p-TPD=4-tetrazoylpyridine,p-HTPD=protonated 4-tetrazoylpyridine)以及Ln(H2O)8·3(m-TPD)·6H2O(m-TPD=3-tetrazoylpyridine,Ln=Yb(4))。X-射线单晶结构分析显示,在配合物1~4中,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(A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(B层)。固态荧光分析表明,配合物1,2,4在405、400、494 nm处出现了最大强度的发射峰值;而配合物3在618、592及462 nm出现了最大强度的发射峰值。热重分析表明配合物1~4在70~120℃范围内有1个失重,而在180~220℃范围内配合物开始分解。
By the reaction of cyanopyridine (4-cyanopyridine and 3-cyanopyridine) with rare earth nitrate (Ln = Nd, Eu and Yb), four rare earth (Ln = Nd (1), Eu (2), Yb (3)), p-HTPD, TPD = 4-tetrazoylpyridine, p-HTPD = protonated 4-tetrazoylpyridine and Ln (H2O) 8.3 (m-TPD) 6H2O (m-TPD = 3-tetrazoylpyridine, Ln = Yb (4)). X-ray single crystal structure analysis showed that in complexes 1 ~ 4, rare earth metal ions and ligands are in two different layers, [Ln (H2O) 8] 3+ structural units and p-TPD and water molecules through hydrogen Bond to form a cation layer (layer A), while p-TPD and p-HTPD form an anion layer (layer B) via π-π stacking and hydrogen bonding. Solid-state fluorescence analysis showed that the complexes 1, 2 and 4 exhibited the maximum intensity emission peak at 405,400 and 494 nm, while the complex 3 peaked at maximum intensity at 618,592 and 462 nm. Thermogravimetric analysis showed that complexes 1 ~ 4 have one weight loss in the range of 70 ~ 120 ℃, while the complexes begin to decompose in the range of 180 ~ 220 ℃.