Keggin 型多酸诱导合成的两个超分子化合物的水热制备

摘要

报道了两例水热条件下合成的Keggin 型多金属氧酸盐和柔性双吡啶四氮唑配体构筑的多酸基超分子化合物：[La1．5PMo12O40]（1）（La ＝1，4－双（5－（3－吡啶基）－四唑基）丁烷）和[Lb2SiMo12O40]（2）（Lb ＝1，3－双（5－（3－吡啶基）－四唑基）丙烷），并通过单晶X－射线衍射、元素分析和红外光谱对两种晶体进行了表征．结构分析表明化合物1属于三斜晶系， P 1空间群，晶胞参数a＝13．575（5）Å，b＝14．060（5）Å，c＝15．754（5）Å，α＝73．136（5）°，β＝80．084（5）°，γ＝73．048（5）°，V＝2739．9（17）Å3，Z＝2，R1＝0．0529，ωR2＝0．1407．化合物2属于正交晶系，Cmca空间群，晶胞参数a＝23．392（5）Å，b＝0．451（5）Å，c＝25．013（5）Å，V＝6115（3）Å3，Z＝4，R1＝0．0395，ωR2＝0．0923．在两个化合物中，Keggin多酸阴离子和有机双吡啶四氮唑配体La和Lb 通过分子间非共价键的氢键弱作用连接形成超分子网络．我们研究了两个化合物的电化学和光催化性能．%Under hydrothermal conditions two supramolecular compounds based on Keggin and flexible bis (Tetrazol-pyridine) ligands have been synthesized, [La1.5PMo12O40] (1) (La=1,1'-(1,4-butanediyl)bis (3-(2H-Tetrazol-5-yl) -pyridine)) and [Lb2SiMo12O40] (2) (Lb =1,1'-(1,3-propane)bis(3-(2H-Tetrazol-5-yl) -pyridine)) characterized by single -crystal X -ray diffraction, elemental analyses and IR spectra.Structural analysis shows that compound 1 crystallizes in space group P 1, a=13.575(5)Å,b=14.060(5)Å,c=15.754(5)Å,α=73.136(5) °,β=80.084(5) °,γ=73.048(5)°,V=2739.9(17)Å3,Z=2,R1 =0.0529,ωR2 =0.1407.Compound 2 crystallizes in space group Cmca , a=23.392(5)Å,b=0.451 (5)Å,c=25.013(5)Å,V=6115(3)Å3 ,Z=4,R1 =0.0395,ωR2 =0.0923.In these two compounds , the Keg-gin polyoxoanions and bis ( Tetrazol-pyridine ) ligands La and Lb link each other through hydrogen bonding in-teractions to construct supramolecular networks .We studied the electrochemical and photocatalytic properties of 1 and 2 .