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首页> 外文期刊>Chemistry: A European journal >Crown-Shaped Tungstogermanates as Solvent-Controlled Dual Systems in the Formation of Vesicle-Like Assemblies
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Crown-Shaped Tungstogermanates as Solvent-Controlled Dual Systems in the Formation of Vesicle-Like Assemblies

机译：冠状钨锗锗酸盐在类泡状组件的形成中为溶剂控制的双系统

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摘要

Reaction of early lanthanides, GeO2, and Na2WO4 in a NaOAc buffer results in large crown-shaped polyoxometalates based on [Ln(2)GeW(10)O(38)](6-) subunits. By using Ni2+ as a crystallizing agent, [Na subset of Ln(12)Ge(6)W(60)O(228)(H2O)(24)](35-) (Na subset of Ln(12)) hexamers formed by alternating beta(1,5)/beta(1,8) subunits were obtained for Ln=Pr, Nd. The addition of K+ led to a similar anion for Ln=Sm, namely, [K subset of Sm12Ge6W60O228(H2O)(22)](35)- (K subset of Sm-12) and [K subset of K(7)Ln(24)Ge(12)W(120)O(444)(OH)(12)(H2O)(64)](52)- (K subset of Ln(24)) dodecamers that consist of a central core identical to K subset of Sm-12 decorated with six external gamma(3,4) subunits for Ln=Pr, Nd. These anions dissociate in water into hexameric cores and monomeric entities, as shown by ESI mass spectrometry. The former self-as-semble into spherical, hollow, and single-layered blackberry-type structures with radii of approximately 75 nm, as monitored by laser light scattering (LLS) and TEM techniques. Analogous studies performed for K subset of Nd-24 in water/acetone mixtures show that the dodecamers remain stable and form in turn their own type of blackberries with sizes that increase from approximately 20 to 50 nm with increasing acetone content. This control over both the composition and size of the vesicle-like assemblies is achieved for the first time by modifying the architecture of the species that undergoes supramolecular association through the solvent polarity.
机译：早期镧系元素，GeO2和Na2WO4在NaOAc缓冲液中的反应导致基于[Ln（2）GeW（10）O（38）]（6-）亚基的大冠状多金属氧酸盐。通过使用Ni2 +作为结晶剂，[Ln（12）Ge（6）W（60）O（228）（H2O）（24）的Na子集）（35-）（Ln（12）的Na子集）六聚体形成通过交替的beta（1,5）/ beta（1,8）亚基获得Ln = Pr，Nd。 K +的添加导致Ln = Sm的阴离子相似，即[Sm12Ge6W60O228（H2O）（22）的K子集] [35）-（Sm-12的K子集）和[K（7）Ln的K子集（24）Ge（12）W（120）O（444）（OH）（12）（H2O）（64）]（52）-（Ln（24）的K个子集）十二聚体，其中心核与Sm-12的K个子集装饰有六个外部gamma（3,4）子单元，用于Ln = Pr，Nd。这些阴离子在水中分解为六聚体核和单体实体，如ESI质谱所示。通过激光散射（LLS）和TEM技术监测，前者自组装成半径约为75 nm的球形，中空和单层黑莓型结构。对Nd-24在水/丙酮混合物中的K子集进行的类似研究表明，十二聚体保持稳定并依次形成其自身类型的黑莓，随着丙酮含量的增加，黑莓的尺寸从约20 nm增加到50 nm。通过修饰通过溶剂极性经历超分子缔合的物质的结构，首次实现了对囊样组合物的组成和大小的控制。

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