<br>具有一个中心钾阳离子的普雷斯勒型磷钨酸盐的制备以及钾阳离子迁移到普雷斯勒分子中形成二钾包封衍生物,ACS Omega

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具有一个中心钾阳离子的普雷斯勒型磷钨酸盐的制备以及钾阳离子迁移到普雷斯勒分子中形成二钾包封衍生物
ACS Omega ( IF 3.7 ) Pub Date : 2018-02-27 00:00:00 , DOI: 10.1021/acsomega.8b00163
Akio Hayashi ₁ , Muh Nur Khoiru Wihadi ₁ , Hiromi Ota ₂ , Xavier López ₃ , Katsuya Ichihashi ₄ , Sadafumi Nishihara _{4,

4,

4} , Katsuya Inoue _{4,

4,

4} , Nao Tsunoji ₁ , Tsuneji Sano ₁ , Masahiro Sadakane ₁

Affiliation

单钾阳离子包封的普赖斯勒型磷钨酸盐 [P ₅ W ₃₀ O ₁₁₀ K] ^14– ( 1 )，通过以下方法制备为钾盐 K ₁₄ [P ₅ W ₃₀ O ₁₁₀ K] ( 1a )加热单铋或单钙封装的普赖斯勒型磷钨酸盐（K ₁₂ [P ₅ W ₃₀ O ₁₁₀ Bi(H ₂ O)] 或 K ₁₃ [P ₅ W ₃₀ O ₁₁₀ Ca(H ₂ O)]）在醋酸盐缓冲液中。通过单晶 X 射线结构分析、 ³¹ P 和¹⁸³ W 核磁共振 (NMR) 光谱、傅里叶变换红外光谱、高分辨率电喷雾电离质谱和元素分析对钾盐1a进行表征，表明一种钾阳离子被封装在具有形式D _{5 h}对称性的 Preyssler 型磷钨酸盐分子的中心空腔中。密度泛函理论计算证实，钾阳离子更喜欢空腔的中心位置而不是侧面位置，在侧面位置没有水分子与封装的钾阳离子配位。 ³¹ P NMR 和循环伏安分析表明，与其他普雷斯勒型化合物相比，空腔中氧的质子化-去质子化速度较快。加热固态的1a得到二 K ⁺包封的化合物 K ₁₃ [P ₅ W ₃₀ O ₁₁₀ K ₂ ] ( 2a )，表明钾抗衡阳离子被引入侧腔之一，同时将内部钾离子从中心转移到第二个侧腔，从而提供了一种在普雷斯勒化合物中封装额外阳离子的新方法。

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Preparation of Preyssler-type Phosphotungstate with One Central Potassium Cation and Potassium Cation Migration into the Preyssler Molecule to form Di-Potassium-Encapsulated Derivative

A mono-potassium cation-encapsulated Preyssler-type phosphotungstate, [P₅W₃₀O₁₁₀K]^14– (1), was prepared as a potassium salt, K₁₄[P₅W₃₀O₁₁₀K] (1a), by heating mono-bismuth- or mono-calcium-encapsulated Preyssler-type phosphotungstates (K₁₂[P₅W₃₀O₁₁₀Bi(H₂O)] or K₁₃[P₅W₃₀O₁₁₀Ca(H₂O)]) in acetate buffer. Characterization of the potassium salt 1a by single-crystal X-ray structure analysis, ³¹P and ¹⁸³W nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared spectroscopy, high-resolution electrospray ionization mass spectroscopy, and elemental analysis revealed that one potassium cation is encapsulated in the central cavity of the Preyssler-type phosphotungstate molecule with a formal D_5h symmetry. Density functional theory calculations have confirmed that the potassium cation prefers the central position of the cavity over a side position, in which no water molecules are coordinated to the encapsulated potassium cation. ³¹P NMR and cyclic voltammetry analyses revealed the rapid protonation–deprotonation of the oxygens in the cavity compared to that of other Preyssler-type compounds. Heating of 1a in the solid state afforded a di-K⁺-encapsulated compound, K₁₃[P₅W₃₀O₁₁₀K₂] (2a), indicating that a potassium counter-cation is introduced in one of the side cavities, concomitantly displacing the internal potassium ion from the center to a second side cavity, thus providing a new method to encapsulate an additional cation in Preyssler compounds.

更新日期：2018-02-27

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